th
The 14 International
Symposium on Inorganic
Ring Systems
July 26th – July 31st 2015
University of Regensburg
93040 Regensburg
Germany
www.iris14.de
Program and Abstracts
IRIS occurs every three years and is the premier international showcase for
Main Group Chemistry, including Organometallic Chemistry and Inorganic
Materials Chemistry. The IRIS meetings bring together leading professors,
postdoctoral fellows and research students from around the world.
The History of IRIS
Year
Town
Country
Host/Chair
IRIS-1
1975
Besancon
France
H. Garcia-Fernandez
IRIS-1b
1977
Madrid
Spain
H. Garcia-Fernandez
IRIS-2
1978
Göttingen
Germany
O. Glemser
IRIS-3
1981
Graz
Austria
E. Hengge
IRIS-4
1985
Paris
France
H. Garcia-Fernandez
IRIS-5
1988
Amherst
Massachusetts, USA
R. R. Holmes
IRIS-6
1991
Berlin
Germany
R. Steudel
IRIS-7
1994
Banff
Alberta, Canada
T. Chivers
IRIS-8
1997
Loughborough
UK
J. D. Woollins
IRIS-9
2000
Saarbrücken
Germany
M. Veith
IRIS-10
2003
Burlington
Vermont, USA
C. Allen
IRIS-11
2006
Oulu
Finland
R. S. Laitinen
IRIS-12
2009
Goa
India
P. Mathur
IRIS-13
2012
Victoria, B.C.
Canada
N. Burford
Message from Nikolaus Korber
Senior Vice President, University of Regensburg
Welcome to the 14th International Symposium on Inorganic Ring
Systems and welcome to Regensburg. The University of
Regensburg is honored to be hosting the premier international forum
for Main Group Chemistry. The IRIS-14 conference provides an
excellent opportunity to raise national and international
collaboration in this important research field. Chemistry plays a
central role in many of the University of Regensburg’s research
strengths. Our highly successful and internationally recognized
Faculty of Chemistry and Pharmacy is excited to organize IRIS-14 as showcase for promoting
world-class research and outstanding chemical education. I hope you will enjoy your time
with us in Regensburg. Our city also has a special historical link to chemistry: Albert the
Great, author of the first medieval chemical textbook “De Mineralibus” and discoverer of the
element arsenic, was bishop of Regensburg from 1260 to 1262.
Prof. Dr. Nikolaus Korber
Senior Vice President
University of Regensburg
Welcome Message from Manfred Scheer
Symposium Chair
Welcome to the 14th International Conference on Inorganic Ring
Systems and welcome to the historic city of Regensburg. Located on
the northernmost point of the Danube River, the old town of
Regensburg together with the suburb Stadtamhof is an exceptional
example of a Central European medieval trading centre. The rich
interchange of cultural and architectural influences can be seen
across the city until this day. Regensburg’s 11th- to 13th-century
architecture still defines the character of the town. The historic
buildings include medieval patrician houses and towers, a large number of churches and
monastic ensembles, including St. Peter’s Cathedral, as well as the 12th-century Stone Bridge.
Since July 2006, Regensburg has been inscribed on the UNESCO list of World Heritage Sites.
Nevertheless, with more than 155,000 inhabitants and almost 30,000 students, Regensburg is
a young and modern city. The University of Regensburg, founded in 1962, is located south of
the downtown area. On its campus IRIS-14 will take place.
The program of the conference starts with an opening mixer on Sunday evening at the Old
Town Hall, which was home to the so-called “Eternal Diet”, the parliament of the Holy
Roman Empire, for two centuries from 1663 until 1806. The scientific oral presentations (25
plenary and keynote lectures and 63 oral presentations) are scheduled from Monday morning
to Friday noon, with poster sessions (175 posters) on Monday and Tuesday evening. I am
grateful for the excellent advice and support of my colleagues on the International Advisory
Board, the National Advisory Committee and the Local Organizing Committee during the
development of this exciting program. On Wednesday afternoon there will be an excursion in
the form of a boat trip on the Danube to the Walhalla memorial (neo-classical German hall of
fame), and on Thursday evening the symposium banquet will take place in the Minorites
Church, which is part of the Historical Museum of the City of Regensburg. I hope all of the
342 participants from 22 countries will very much enjoy this great meeting of contemporary
main group chemistry.
We are grateful for the financial support of the sponsors who have contributed to this event.
Manfred Scheer
Symposium Chair
University of Regensburg
The organizers acknowledge the generous support of the following
sponsors:
IRIS-14 International Advisory Board
C. W. Allen (USA)
M. Scheer (Germany)
T. Chivers (Canada)
R. Streubel (Germany)
A. H. Cowley (USA)
N. Tokitoh (Japan)
R. R. Holmes (USA)
R. Uhlig (Austria)
R. Laitinen (Finland)
M. Veith (Germany)
N. Burford (Canada)
R. West (USA)
P. Mathur (India)
J. D. Woollins (UK)
H. W. Roesky (Germany)
IRIS-14 National Advisory Committee
J. Beckmann (Bremen)
D. Scheschkewitz (Saarbrücken)
H. Braunschweig (Würzburg)
A. Schnepf (Tübingen)
R. Breher (Karlsruhe)
A. Schulz (Rostock)
S. Dehnen (Marburg)
U. Siemeling (Kassel)
D. Gudat (Stuttgart)
D. Stalke (Göttingen)
S. Harder (Erlangen)
R. Streubel (Bonn)
E. Hey-Hawkins (Leipzig)
W. Uhl (Münster)
K. Jurkschat (Dortmund)
M. Wagner (Frankfurt/M.)
M. Mehring (Chemnitz)
J. Weigand (Dresden)
R. Pietschnig (Kassel)
IRIS-14 Local Organizing Committee
Manfred Scheer, Symposium Chair
Gábor Balázs
Karin Kilgert
Eva-Maria Rummel
With additional contribution of
Robert Kretschmer
Christian Marquardt
Martina Amann
Daniela Meyer
Katharina Baier
Moritz Modl
Michael Bodensteiner
Julian Müller
Jens Braese
Eugenia Peresypkina
Helena Brake
Felix Riedlberger
Luis Duetsch
Reinhard Rund
Mehdi Elsayed Moussa
Thomas Schottenhammer
Martin Fleischmann
Monika Schmidt
Oliver Hegen
Andrea Schreiner
Claudia Heindl
Michael Seidl
Tobias Kahoun
Andreas Seitz
David Konieczny
Fabian Spitzer
Barbara Krämer
Andreas Stauber
Giuliano Lassandro
Valentin Vass
Petra Lugauer
Alexander Virovets
Eric Mädl
Rudolf Weinzierl
IRIS-14 Schedule of Events at a Glance
Sunday, July 26th
8:30
8:50
9:00
9:10
9:20
9:30
9:40
9:50
10:00
10:10
10:20
10:30
10:40
10:50
11:00
11:10
11:20
11:30
11:40
11:50
12:00
12:10
12:20
12:30
Monday, July 27th
Registration
Welcome
Tuesday, July 28th
Wednesday, July 29th
Registration
Registration
PL1
R. Mulvey
PL3
C. Cummins
PL5
H. Grützmacher
PL7
T. Fäßler
KL1
H. Braunschweig
KL4
E. Hevia
KL7
C. Jones
KL10
I. Manners
KL2
A. Schulz
KL5
G. Bertrand
KL8
C-W. Chiu
KL11
E. Rivard
KL14
J. Goicoechea
Coffee Break
Coffee Break
Coffee Break
Coffee Break
KL15
S. Harder
KL6
D. Scheschkewitz
KL9
G. Robinson
KL12
S. Yamaguchi
Coffee Break
PL4
D. Stephan
PL6
F. Gabbaï
KL13
L. Berben
KL16
I. Krossing
PL2
N. Burford
KL3
D. Bourissou
12:10 – 1:40
Lunch
Thursday, July 30th
PL8
S. Aldridge
12:00 – 1:40
Lunch
12:10 – 1:40
Lunch
----13:40
13:50
14:00
14:10
14:20
14:30
14:40
14:50
15:00
15:10
15:20
15:30
15:40
15:50
16:00
16:10
16:20
16:30
16:40
16:50
17:00
----19:00
21:00
16:00
Registration
A1
C. Russell
A2
D. P. Gates
A3
F. Dielmann
A4
J. Weigand
A5
P. Pringle
B1
M. Beckett
B2
T. Agou
B3
A. Timoshkin
B4
H. Bettinger
B5
A. Ruzicka
A10
R. Streubel
A11
L. Nyulaszi
A12
E. Hey-Hawkins
A13
R. Pietschnig
A14
F. Uhlig
B10
S. Konchenko
B11
R. Layfield
B12
L. Dostal
B13
R. Waterman
B14
D. Gudat
C1
G. Balázs
C2
R. Murugavel
C3
J. Corrigan
C4
C. Strohmann
C5
B. Ramamoorthy
Coffee Break
Coffee Break
Coffee Break
Coffee Break
A6
W. Uhl
A7
C. Slootweg
A8
R. Kretschmer
A9
R. Melen
B6
T. Chivers
B7
Y. Yamamoto
B8
A. Zibarev
B9
I. Vargas-Baca
A15
R. Fischer
A16
R. Wolf
A17
V. Lee
A18
U. Siemling
B15
J. Beckmann
B16
M. Cowley
B17
W. Kaim
B18
I. Bezkishko
Poster Session A
Opening
Poster Session B
A19
T. Müller
A20
T. Iwamoto
A21
T. Sasamori
A22
L. Wesemann
A23
M. Saito
B19
T. Baumgärtner
B20
M. Veith
B21
D. Stalke
B22
R. Boeré
B23
C. Macdonald
Coffee Break
Coffee Break
Coffee Break
C6
C. Tessier
C7
Z. Benkö
C8
M. Mosquera
C9
G. Mloston
A24
A. Schnepf
A25
S. Dehnen
A26
C.-W. So
A27
K. Jurkschat
B24
C. Lescop
B25
C. Romero-Nieto
B26
H. Stueger
B27
M. Balakrishna
14:00-19:00
Excursion
July Friday, 31st
19:00-23:00
Banquet
KL17
N. Tokitoh
12:30 – 13:00
Closing remarks
Registration, Lunches and Social Events
Registration
Sunday, July 26th
4:00-7:00 p.m.
Monday, July 27th
8:30-9:00 a.m.
Tuesday, July 28th
8:30-9:00 a.m.
Wednesday, July 29th
8:30-9:00 a.m.
Thursday, July 30th
8:30-9:00 a.m.
at the Old Town Hall,
Rathausplatz 1, 93053 Regensburg
at the University of Regensburg,
in the lobby of the central lecture hall H1
at the University of Regensburg,
in the lobby of lecture hall H24
Opening Mixer
Sunday, July 26th,
7:00-9:00 p.m.
at the Old Town Hall,
Rathausplatz 1, 93053 Regensburg
Lunch
Monday, July 27th
12:10-1:40 p.m.
Tuesday, July 28th
12:10-1:40 p.m.
Wednesday, July 29th
12:00 p.m.
at the University of Regensburg, in the lobby
of lecture hall H24 (Lunchbox)
Thursday, July 30th
12:10-1:40 p.m.
at the University of Regensburg,
in the lobby of the central lecture hall H1
at the University of Regensburg,
in the lobby of the central lecture hall H1
Boat Trip on the Danube
to the Walhalla with the “Kristallkönigin” (crystal queen) boat:
Wednesday, July 29th, 2:00 p.m., boarding and landing at the “Eiserne Brücke”
Conference Dinner
Thursday, July 30th, 7:00-9:00 p.m. at Minoritenkirche (Minorites Church, part of the Historic
Museum of the City of Regensburg), Dachauplatz 2-4, 93047 Regensburg
Scientific
Program
Timetable
Monday, July 27th
H1
Chair: M. Scheer
PL01 9:00
Robert E. Mulvey
KL01 9:40
Holger Braunschweig
KL02 10:10 Axel Schulz
Template Ring Approaches to Metallation Chemistry
Cyclic and Acyclic Boron-based Chromophores: Highly
Unusual Donor-Acceptor Systems
Activation of Small Molecules by Biradicaloids
10:40 Coffee Break
H1
Chair: W. Uhl
PL02 11:00 Neil Burford
KL03 11:40 Didier Bourissou
Evolving the Coordination Chemistry of p-Block
Element Lewis Acceptors
Boron-Cations and Radicals Stabilized by Strong P→B
Interactions
Lunch
H2
Chair: E. HeyHawkins
A01
13:40 Chris Russell
A02
14:00 Derek P. Gates
A03
14:20 Fabian Dielmann
A04
14:40 Jan J. Weigand
A05
15:00 Paul Pringle
H3
Main Group Elements as Transition Metals: Reactions of
Phosphorus-Carbon Multiple Bonds with Small
Molecules
The Addition-Isomerization Polymerization of
Phosphaalkenes
Highly electron-rich phosphines for the activation of
small molecules
Synthesis and Reactivity of a Zwitterionic
Diphosphanide
'Inorganic' Arylphosphines
Chair: D. Stalke
B01
13:40 Michael Beckett
B02
14:00 Tomohiro Agou
B03
14:20 Alexey Timoshkin
B04
14:40 Holger Bettinger
B05
15:00 Ales Ruzicka
New isolated polyborate anions templated by cationic
transition-metal complexes
Reactivities of a Barrelene-type Dialumane as an
Equivalent of an Al=Al Doubly-bonded Species
Donor-acceptor complexes of inorganic analogs of
benzene
Multiply Boron-Nitrogen Doped Hexi-perihexabenzocoronene
Main group metal complexes containing hybrid
amino/guanidinate (1- or 2-) ligands
15:20 Coffee Break
Scientific Program
H2
Chair: S. Dehnen
A06
15:40 Werner Uhl
A07
16:00 Chris Slootweg
A08
16:20 Robert Kretschmer
A09
16:40 Rebecca Melen
H3
An Al/P Based Frustrated Lewis Pair as an Efficient
Ambiphilic Ligand for the Coordination and Activation
of Polar Compounds
Cooperative Lewis Acid/Base Catalysis
Subsequent Reduction of a Cyclic Alkyl (amino)
carbene–SbCl3 Adduct – Access to Different Oxidation
States of Antimony
Activation of π-Bonds Towards Cyclization Reactions
using Lewis Acidic Boranes
Chair: C. Allen
B06
15:40 Tristram Chivers
B07
16:00 Yohsuke Yamamoto
B08
16:20 Andrey Zibarev
B09
16:40 Ignacio Vargas-Baca
17:00 Poster Presentations
Chalcogen Macrocycles Incorporating P2N2 Rings and
Coinage Metals
Synthesis and Properties of Hypervalent Sulfur Radicals
Synthesis and Characterization of Sulfur-Nitrogen πHeterocyclic Radical-Anion Salts with Sandwich
Organometallic Cations
The Supramolecular Chemistry of Iso-Tellurazole NOxides
Uneven numbered Posters
Scientific Program
Tuesday, July 28th
H1
Chair: F. Gabbai
PL03 9:00
Christopher C. Cummins
KL04 9:40
Eva Hevia
KL05 10:10 Guy Bertrand
Phosphorus-Containing Ring Systems from Low to High
Oxidation States
New main group-metal-mediated strategies for ring
functionalisation
Nucleophilic boron derivatives, stable phosphinidenes
and other main group species
10:40 Coffee Break
H1
Chair: R. Mulvey
KL06 11:00 David Scheschkewitz
PL04 11:30 Doug Stephan
Base-Induced Isomerization of Unsaturated Group 14
Ring Systems
FLP-rings: Applications in Synthesis and Catalysis
Lunch
H2
Chair:
D. Scheschkewitz
A10
13:40 Rainer Streubel
A11
14:00 Laszlo Nyulaszi
A12
14:20 Evamarie Hey-Hawkins
A13
14:40 Rudolf Pietschnig
A14
15:00 Frank Uhlig
H3
Building Blocks for Smart Inorganic Polymers
(SIPs CM1302)
Super-strained inorganic ligands: substrate-dependent
reactivity
Hetero deoxy-Breslow intermediates – and more
Unusual Reactivity of Alkali Metal
Oligophosphanediides
Stable Silanetriols – Building Blocks for Rings and
Cages
Cyclic Derivatives of Group 14 in Material Science
Chair: C. Russell
B10
13:40 Sergey Konchenko
B11
14:00 Richard Layfield
B12
14:20 Libor Dostál
B13
14:40 Rory Waterman
B14
15:00 Dietrich Gudat
Mixed d-/f-Metal Polypnictide Complexes
Phosphorus, Arsenic and Antimony Ligands in
Lanthanide Molecular Nanomagnets
Quest for Monomeric Stibinidenes and Bismuthinidenes
as New Ligands for Transition Metals
Iron-Catalyzed Routes to Phosphorous-Containing Rings
One, two, three Halogens on the Ring - on the Formation
Mechanism of N-Heterocyclic Haloboranes and
Halophosphanes
Scientific Program
H4
Chair: K. Jurkschat
Complexes Containing W≡E (E = P, As and Sb) Triple
Bond as Precursors for Linearly Coordinated EQ (Q = O,
S, Se and Te) Ligands
Is Single-4-Ring the Most Basic but Elusive Secondary
Ramaswamy Murugavel Building Unit that Transforms to Larger Structures in
Zinc Phosphate Chemistry?
NHC Ligands for Ternary Metal-Chalcogen Cluster
John F. Corrigan
Assembly
Reactivity and Structure-Building Principles of LiCKOR
Carsten Strohmann
Base Mixtures in THF
Boomi Shankar
Functional metal-organic molecules and materials
Ramamoorthy
derived from rigid and flexible P-N scaffolds
C1
13:40 Gábor Balázs
C2
14:00
C3
14:20
C4
14:40
C5
15:00
15:20 Coffee Break
H2
Chair: T. Chivers
A15 15:40 Roland C. Fischer
A16 16:00 Robert Wolf
A17 16:20 Vladimir Lee
A18 16:40 Ulrich Siemeling
H3
Chair: R. Layfield
B15 15:40 Jens Beckmann
B16 16:00 Michael J. Cowley
B17 16:20 Wolfgang Kaim
B18 16:40 Ilya Bezkishko
H4
15:40 Claire Tessier
C7
16:00 Zoltán Benkö
Marta Elena Gonzalez
16:20
Mosquera
C9
Peri-Interactions within (Ace)Naphthyl Compounds
Reloaded
Synthesis and reactivity of phosphinidene boranes
Unconventional Ring Sizes with Noninnocent Ligand
Components
The sodium 3,4,5-triaryl-1,2diphosphacyclopentadienides derivatives: synthesis and
coordination properties
Chair: R. Streubel
C6
C8
Captivating Organotin Anions – Cages, Rings and
Chains
Transformations of Small Inorganic Molecules by Lowvalent Transition Metalate Anions and Transition Metal
Radicals
Pyramidanes: the Covalent Form of an Ionic Compound
Stable N-Heterocyclic Carbenes with a 1,1’Ferrocenediyl Backbone and Their Heavier Homologues
16:40 Grzegorz Mloston
17:00 Poster Presentations
Chlorine/oxygen transfer reactions of [PCl2N]3 using
oxygenated Lewis bases as a possible route to [PON]3
Phosphorus heterocycles from Na(OCP)
Terpene Main Group Chiral Derivatives: Catalytic
Activity in Polymerization and C-H Activation Processes
Ferrocenyl Substituted 1,3-Dithiolanes via [3+2]Cycloadditions of Thiocarbonyl S-Methanides with
Ferrocenyl/Hetaryl Thioketones
Even numbered Posters
Scientific Program
Wednesday, July 29th
H24 Chair: N. Burford
PL05
9:00 Hansjörg Grützmacher
KL07 9:40 Cameron Jones
KL08 10:10 Ching-Wen Chiu
New Phosphorus Heterocycles from Simple Building
Blocks
Low oxidation state main group compounds: stabilisation
strategies and transition metal-like reactivity
Boron Cations and Poly-dentate Divalent Group 14
Ligands
10:40 Coffee Break
H24 Chair: G. Bertrand
KL09 11:00 Greg Robinson
PL06 11:30 François Gabbaï
From Metalloaromaticity to N-Heterocyclic Carbenes:
The Evolution of Inorganic Rings
Lewis acidic and redox properties of organoantimony
derivatives – Applications in anion sensing and halogen
photoreductive elimination
Lunch
14:00 Boat trip
Scientific Program
Thursday, July 30th
H24 Chair: I. Krossing
PL07
9:00 Thomas Fässler
KL10 9:40 Ian Manners
KL11 10:10 Eric Rivard
Group 14 element rich cages and rings as precursors and
intermediates for the formation of intermetalloid clusters
Catalysis in Service of Main Group Chemistry: MetalMediated and Metal-Free Routes to Molecules and
Materials based on Elements from Group 13-15
Inorganic Heterocycles: From New Light-emitting
Entities to Surprising Products from Ligand Activation
10:40 Coffee Break
H24 Chair: M. Veith
KL12 11:00 Shigehiro Yamaguchi
Main group strategy for photo and electronic functions
KL13 11:30 Louise Berben
Ligand-Based Redox Chemistry with Aluminum(III)
Lunch
H43 Chair: D. Gudat
A19
13:40 Thomas Müller
A20
14:00 Takeaki Iwamoto
A21
14:20 Takahiro Sasamori
A22
14:40 Lars Wesemann
A23
15:00 Masaichi Saito
Transformations of Small Inorganic Molecules by Lowvalent Transition Metalate Anions and Transition Metal
Radicals
Reactions of tricyclopentasilane and related cyclic
silicon compounds with bulky alkyl substituents
Synthesis of 1,2-Digermacyclobutene Derivatives and
Their Reactions with Ethylene
Synthesis, Molecular Structure and Reactivity of Cyclic
Sn–P-Lewis Pairs
Synthesis, Structures and Reactions of Antiaromatic
Organolead Compounds Stabilized by Lewis Bases
H44 Chair: D. Woollins
B19
13:40 Thomas Baumgartner
B20
14:00 Michael Veith
B21
14:20 Dietmar Stalke
B22
14:40 René Boeré
B23
15:00 Charles Macdonald
Laterally-Functionalized Phospholes – Versatile
Building Blocks for π-Conjugated Materials
From cyclic and polycyclic alkoxoaluminium hydrides to
alumina composites with nano- and micro-meter rings
and cages
A World of Difference – Alkali Metal Organic
Frameworks From Ammonia
Coordination Polymers from Main Group Ring
Compounds
Ligand Chemistry of Stable Phosphorus(I) Compounds
15:20 Coffee Break
Scientific Program
H43 Chair: L. Wesemann
A24
15:40 Andreas Schnepf
Chemistry Applying Metalloid Tin Clusters
Ternary Intermetalloid Clusters: About Unexpected
Structures and How to Get There
Base-Stabilized Low Valent Group 14 Element
Complexes for the Construction of Unsaturated Systems
Anion and Cation Complexation by Di- and
Multicentered Tin-Based Lewis Acids
A25
16:00 Stefanie Dehnen
A26
16:20 Cheuk-Wai So
A27
16:40 Klaus Jurkschat
B24
Chair: T.
Baumgärtner
15:40 Christophe Lescop
B25
16:00 Carlos Romero-Nieto
B26
16:20 Harald Stueger
B27
16:40 Maravanji Balakrishna Cyclodiphosphazanes in Metal Organic Frameworks
H44
Thermochromic Emissive Metallacycles
Paving the Way to Novel Phosphorus-based
Architectures: a Non-catalyzed Protocol to Access Fused
Heterocycles
Photoinduced Rearrangement of Acylcyclopolysilanes
19:00 Conference Dinner
Scientific Program
Friday, 31 July
H24 Chair: C. Jones
PL08
9:30 Simon Aldridge
KL14 10:10 Jose Goicoechea
KL15 10:40 Sjoerd Harder
Novel approaches to E-H bond activation and
functionalization using Main Group systems
Novel Phosphorus ring systems derived from the 2phosphaethynolate anion
Early Main Group Metal Hydride Complexes
11:10 Coffee Break
H24 Chair: T. Fäßler
KL16 11:30 Ingo Krossing
KL17 12:00 Norihiro Tokitoh
Bermuda-Clusters…? On the Interaction of Chelating
Bipyridines with Subvalent Ga+ and In+ Salts of the
[Al(ORF)4]– WCA
New Aspects in the Chemistry of Al-containing Cyclic
Compounds
12:30 Closing Remarks
Scientific Program
Contributed Poster Presentations
Poster no
P001
P002
P003
P004
P005
P006
P007
P008
P009
P010
P011
P012
P013
P014
P015
P016
P017
P018
P019
P020
P021
P022
P023
P024
P025
P026
Presenter
Naoki Ando
Evgeny Kolychev
Title of the Abstract
Photocyclization of Dimesitylborylarenes
Chelating bis(diazaboryl) ligands for preparation of cyclic
bisboryl complexes
Jesus Campos
Synthetic Applications of Borylzinc Compounds: Boryl Transfer
Manzano
Chemistry and Catalytic Borylation.
Harmen Zijlstra
Well-Defined Boralumoxanes as Convenient MAO Modelling
Compounds
Charlotte Jones
Syntheses, structural characterization and DFT investigations of
pentaborate salts templated by substituted pyrrolidinium cations
Jiří Böserle
Study of reactivity of germylene stabilized by boraguanidinate
ligand
Koichi Nagata
Reactions of a Barrelene-type Dialumane Bearing Bulky Aryl
Substituents with Lewis Bases
Tomas Chlupaty
In-Situ Activation of C-C Multiple Bonds Mediated by
Amidinato-Aluminium Framework
María Teresa Muñoz- New aluminate compounds of low nuclearity: synthesis and
Fernández
catalytic activity studies.
Mahendra Kumar
Aminotroponate ligand stabilized pentacoordinate Aluminium
Sharma
(III) complexes
Glen Briand
“Strained” Metal Bonding Environments in Indium(III)
Dithiolates and Their Use as Lewis Acid Catalysts
Daniel Franz
Aluminacycles Derived from the Imidazolin-2-iminato Ligand
Manuel Kapitein
NHC-stabilized Silylphosphinoalanes / -gallanes
Tomáš Řičica
Reactivity of N→Ga Coordinated Organogallium compounds
Katharina Hanau
Synthesis of Gallium Chalcogenide Clusters with Organic
Functionality
Jana Weßing
Hume-Rothery Phase-inspired molecular chemistry – Synthesis
of intermetalloid transition metal/group 13 clusters
Andreas Kirchmeier
The impact of silyl-groups in β-position on the electronic
systems of phospholes
Marius Arz
n and π Complexes of NHC-stabilized Disilicon(0)
Henning
A H-substituted Silylium Ion
Großekappenberg
Fabian Uhlemann
[Si3Cl5(NHC)3]+: An unprecedented Silyl Cation obtained from
metastable SiCl2 Solution
Dennis Lutters
Activation of 7-Silanorbornadienes by NHCs – A Fast and
Selective Way to NHC Stabilized Hydridosilylenes
Yuk Chi Chan
Synthesis and Reactivity of an NHC-stabilized Silicon(I) Dimer
Isabell Omlor
The Silyldisilene-Cyclotrisilane Equilibrium
Hui Zhao
Reactivity of cyclotrisilene with multiply-bonded molecules
Bernhard Baars
Metal-Silicon Triple Bonds: [2+2] Cycloadditions of Alkynes
and Heteroalkynes
Dominik Keiper
Consecutive Synthesis of Novel Cagelike Bicyclic Trisiloxanes
Poster Contributions
Poster no
P027
Presenter
Priyabrata Ghana
P028
Carsten Eisenhut
P029
P030
Miroslav Novák
Kerstin Hansen
P031
Nora Breit
P032
Sabrina Khoo
P033
Kirsten Reuter
P034
P035
Leon Van Der Boon
Philipp Willmes
P036
Christa Grogger
P037
Christopher Golz
P038
P039
P040
P041
Tomohiro Sugahara
Crispin Reinhold
Dominik Schnalzer
Michael Haas
P042
Lena Albers
P043
Kathrin Louven
P044
Kai Schwedtmann
P045
Jordan Waters
P046
David Nieder
P047
P048
Zsolt Kelemen
Arnab Rit
P049
P050
P051
Jan Oetzel
Jessica Edrich
Cem Burak Yildiz
P052
Jan Turek
P053
P054
Niklas Rinn
Olga Gapurenko
Title of the Abstract
Metal─Silicon Multiple Bonds: Metallasilylidynes and
Metallasilacumulenes
The Versatile Reactivity of an NHC-stabilized Silicon(II)
Monohydride
Synthesis of Intramolecularly Coordinated Organosilanes
A Highly Reactive “Half-Parent” Phosphasilene and Iminosilane
LSi=EH (E = N, P)
Reactivity of Phosphorus-functionalized Low-valent Silicon
Compounds towards Transition Metal Complexes
A Low Valent Silicon-Rhodium and -Cobalt Four-Membered
Ring
Synthesis and Properties of Silicon Based Crown Ether
Analogues
Configurationally Stable Pentaorganosilicates
Functionalization and Transfer of Unsaturated Si6 Cluster
Compounds
Synthesis and Characterization of Cyclic Acylsilanes Precursors for Brook-Type Cyclic Silenes
2-(Dimethylaminomethyl)-ferrocenyl
Substituted
Silanols,
Disilanolates and Siloxanes: Search for new Intermediates
Synthesis and Structure of a Stable 1,2-Digermabenzene
Sila- and Germacyclopentadienyl Radicals vs. Anions
Photochemical Reactivity of Cyclic Acylgermanes
Synthesis and Characterization of the first relatively stable
Germenolates
Cationic Rearrangements in Polysilanes and Polygermasilanes Subtle Capture of Intermediates
Is Me3SiOK a Substitute for Me3COK in Schlosser’s Base
Mixtures?
Syntheses and Reactions of Cationic 4-Phosphonio Substituted
NHCs
Synthesis and Reactivity of Ditopic Carbanionic N-Heterocyclic
Carbene Complexes
Reactivity of heavier NHC-coordinated Vinylidene Analogues
towards Anionic Nucleophiles
Stability and Structure of Ferrocene based Carbene Analogues
Acyclic Two-Coordinate Cationic Germylenes – Metal Element
Bond Formation
Ferrocene-based Tetrylenes
Cyclic distannene in reaction with terminal alkynes
Reductive Cleavage of the CO Triple Bond by an Anionic
Lowvalent Maingroup Species
A Computational Chemistry Quest for Viable and Stable Tin(0)
Compounds, The Stannylones.
Functional Binary and Ternary Organotin Selenide Clusters
Group 14 element pyramidanes: theoretical studies
Poster Contributions
Poster no
P055
P056
P057
Presenter
Stefan Mitzinger
Roman Jambor
Denis Kargin
P058
P059
Lies Broeckaert
Robert Wilson
P060
Bastian Weinert
P061
P062
P063
O. Kysliak
Tatsumi Ochiai
Jan Vrána
P064
Kilian Krebs
P065
Julia Schneider
P066
Petr Svec
P067
Paul Gray
P068
Christian Sindlinger
P069
P070
P071
P072
Justin Frank Binder
Alexander Hinz
Thomas Robinson
Stefan Weller
P073
P074
Stefan Borucki
Adinarayana Doddi
P075
Otfried Lemp
P076
P077
P078
Stephanie Kosnik
Alicia López
Andarias
Payal Malik
P079
Michael Seidl
P080
Philip Junker
P081
P082
Siu Kwan Lo
Melina Klein
Title of the Abstract
Quantitative Understanding of Multimetallic Cluster Growth
Chemistry of Intramolecularly Coordinated Stannylenes
Stereoselective approaches towards bisphosphano substituted
tetrylenes via [3]-ferrocenophanes
Formation and Functionalization of Intermetalloid Clusters
Reactivity of M/14/15 Intermetalloid Clusters Toward Organic
and Main Group Organometallic Compounds
An Efficient Approach to Ternary Intermetalloid Clusters and
Novel Zintl Ions
Subsequent chemistry of Ge94- Zintl anion
Synthesis and Reactivity of Novel Amino(imino)metallylenes
Bis(amido)phosphanes and their use as ligands for 14th group
metals
η3-Allyl Coordination at Tin(II) – Reactivity towards
Triplebonds
Reversibility in reactions of cyclic distannenes with terminal
alkynes under ambient conditions
C,N-Chelated Organotin(IV) Azides as Precursors for
Substituted Tetrazoles
Preparation and Reactivity of Cationic Germanium(II) and
Tin(II) Donor-Acceptor Complexes
Versatile precursors: Organotin(IV) hydrides as building blocks
for low-valent tin chemistry
Carbene-Stabilized P(I) Cations
The Reactivity of Heavy Group 15 Allyl Analogs
PCO− as a Precursor to Novel P-Containing Heterocycles
Synthesis and chemical studies of Diaza-phosphaferrocenophanes
Ferrocenylene bridged Oligophosphanes
N-Heterocyclic Carbene Phosphinidene and Phosphinidyne
Metal Complexes and their Applications
New Synthetic Approach to the Synthesis of NHCPhosphinidene Compounds
Zwitterionic Triphospheniums as Multidentate Donors
Synthesis and Photophysical Properties of Novel PhosphorusContaining Conjugated Systems
Cycloaddition of P–C Single Bonds? The Case of
Oxaphosphirane Complexes and ortho-Benzochinones
Reactions of the Pentelidene Complexes [Cp*E{W(CO)5}2] (E =
P, As) with Heterocumulenes
1,3,2-Dioxaphosphol-4-enes: synthesis of a novel inorganic ring
system
Synthesis of asymmetric phosphorus diiminopydrine complexes
Synthesis, thermolysis and photochemistry of oxaphosphirane
complexes
Poster Contributions
Poster no
P083
P084
P085
P086
Presenter
Cristina Murcia
García
Christian Roedl
Eva-Maria Rummel
Elif Şenkuytu
P087
Serap Beşli
P088
Yasemin Tümer
P089
Ceylan Mutlu
P090
Aylin Uslu
P091
Markus Blum
P092
Imtiaz Begum
P093
P094
Jan Faßbender
Rosalyn Falconer
P095
Jonas Bresien
P096
Lukas Guggolz
P097
Jaap E. Borger
P098
P099
P100
Fabian Spitzer
Andreas Seitz
Khatera Hazin
P101
René Labbow
P102
P103
P104
Sivathmeehan
Yogendra
Roman Olejník
Andrew Jupp
P105
Martin Fleischmann
P106
Jonathan Dube
P107
Ralf Kather
Title of the Abstract
Fluorinated oxaphosphirane complexes: synthesis, redox
potentials and novel reactions
Bimetallic 1,3 Diphosphacyclobutadiene Sandwich Compounds
Oxidation and Isomerization of Diphosphete Complexes
Structural Properties of Paraben Substituted FluorenylideneDouble Bridged Cyclophosphazenes
The synthesis and characterization of spiro bridged
cyclophosphazene compounds containing two chiral centers
Syntheses, structural characterizations of new phosphazenes
bearing vanillinato and pendant monoferrocenyl groups
The
substitution
reactions
of
a
mono
ansa
fluorodioxycyclotriphosphazene derivative with diols
Cis- and trans-Azole Substituted Cyclotriphosphazene
Derivatives
A new insight into the homolytical bond dissociation of
Tetraaminodiphosphines
Synthesis of P-functional thiazole-2-thiones – precursors for
NHCs?
Exploring the accessibility of thiaphosphirane complexes anew
1,3,5-Triphosphabenzenes: Molecules with a Thirst for
Hydrogen
[ClP(µ-PMes*)]2 – A Versatile Reagent in Phosphorus
Chemistry
Binary, Protonated Seven-Atom Zintl Anions [H2GeP6]2– and
[H2SiP6]2–
Functionalization of P4 using Lewis acid-stabilized
bicyclo[1.1.0]tetraphosphabutane anions
Fixation and liberation of intact E4 tetrahedra (E = P, As)
Functionalization of [Cpʹʹ2Zr(η1:1-P4)]
Synthesis and Application of Weighable Brønsted Acids
Containing Hexacoordinated Phosphorus(V) Anions
N-Trimethylsilylsulfinylamine - Reactivity and Isomerisation
Induced by Lewis Acids
Synthesis and Reactivity of a Triflyloxyphosphonium Dication
Synthesis and Structure of Terdentate Ketoiminate Complexes
A Novel Synthesis of the 2-Phosphaethynolate Anion and
Subsequent Reactivity
Pentaphospha- and Pentaarsaferrocene - A Comparative Study of
Their Coordination Ability Towards Weakly Coordinating
Lewis Acids
Chemistry of Cationic Arsines: A New Class of Electrophilic
Ligands
Reaction of the Lewis acid B(C6F5)3 with [Ph3SbO]2,
Ph2P(O)OH and other Lewis bases containing oxygen acceptor
atoms
Poster Contributions
Poster no
P108
P109
P110
P111
Presenter
Lukas Belter
Monika Schmidt
Iva Vránová
Johanna Heine
P112
P113
Benjamin Ringler
J. Derek Woollins
P114
P117
Lucia-Myongwon
Lee
Bronte Charette
Nikolay
Pushkarevsky
Jamie Ritch
P118
Nikolay Semenov
P119
Jari Konu
P120
Róża Hamera
P121
Mansura Akter
P122
P123
P124
Carsten Donsbach
Silke Santner
Emanuel Hupf
P125
Martin Hejda
P126
Fabian Müller
P127
Titel Jurca
P128
P129
P130
Klara Edel
Peter Grüninger
Christian Marquardt
P131
Tom Stennett
P132
Niels Lichtenberger
P115
P116
Title of the Abstract
Polycyclic Amides with As and Sb
The reactivity of As4 towards transition metal complexes
Stibinidine and Bismuthinidine as ligands for TM
Using Supramolecular Interactions to shape new Halogenido
Bismuthate Materials
Syntheses of Binary Interpnictogenes and their Reactivity
Investigating non-covalent interactions in crowded frameworks
by 77Se and 125Te solid-state NMR
Supramolecular Interactions of 1,2,5-Selenadiazole Derivatives
Exploring new anionic selenium based pincer ligands
Coordination
and
Reduction
of
1,2,5-Telluradiazole
Heterocycles
Coordination Chemistry of Selenium- and Tellurium-Containing
Pincer Ligands
Novel reaction of 1,2,5-chalcogenadiazoles – coordination of
anions by chalcogen atoms
PCP-Bridged, Chalcogen-Centered Ligands: Coordination
Chemistry and Redox Transformations
Ferrocenyl Substituted 1,3-Dithiolanes via [3+2]-Cycloadditions
of Thiocarbonyl S-Methanides with Ferrocenyl/Hetaryl
Thioketones
Synthesis and biological evaluation of new 5-aryl-4,5-dihydro1,3,4-thiadiazole analogues as small molecule antimicrobial
agents
In Search of Heavy Chalcogenido-d10-metallates
Ionothermal Treatment of Chalcogenidometallates
Probing Donor-Acceptor Interactions in peri-Substituted
Diphenylphosphinoacenaphthyl-Element Dichlorides of Group
13 & 15 Elements
Straightforward formation of the unprecedented 5-membered
annulated ring containing the B-N moiety: 1H-2,1benzazaborolyl alkali metal salts, reactivity with electrophiles
and redox behavior
Catalytic Dehydrogenation of Amino Boranes – Formation of
Condensed Borazine Compounds
Titanocene-based Catalysts for Amine Borane Dehydrocoupling:
Studies of the Mechanistic Role of Ti(III) Species and Formation
of Polyaminoboranes
1,2-Azaborine, the BN derivative of ortho-benzyne
Fragmentation vs. Dehydogenation of Borazines
Cationic and Anionic Chains of only Lewis Base Stabilised
Pnictogenylboranes
Cooperative Al/P Lewis Pairs Based on Cationic Aluminium
Complexes
Binary Group 13/14 and 13/15 Zintl Anions and Their Reactions
towards Ternary Intermetalloid Clusters
Poster Contributions
Poster no
P133
Presenter
Eliza Leusmann
P134
P135
Derya Davarci
Jatinder Singh
P136
Peter Bartoš
P137
Chen-Wei Liu
P138
Kamna Sharma
P139
Shabana Khan
P140
P141
Mehdi Elsayed
Moussa
Nanhai Singh
P142
P143
Hung Banh
Kerstin Freitag
P144
Andrew Roberts
P145
P146
Isabell Nußbruch
Katharina Dilchert
P147
Claudia Heindl
P148
P149
P150
P151
P152
Andrew Davies
Maximilian Jost
Francisco Miguel
García-Valle
Ferda Hacivelioglu
Daniel Himmel
P153
Uttam Chakraborty
P154
P155
P156
Miriam Schwab
Eric Maedl
Dirk Herrmann
P157
Robert Wolf
Title of the Abstract
Toward Connection of Aromatics and Ruthenium Complexes to
Tin/Sulfur Clusters
Ag(I) Coordination Polymers of Cyclophosphazenes
Chiral Oxazoline Complexes of Basal Bulky Cobalt Sandwich
Compounds and Cyclophosphazenes
Luminescent complexes of copper(I) halides with functionalized
tertiary phosphines
Self-Assembly of
a
Luminescent
Thiolato-Stabilized
Hexanonacontanuclear Cuprous Wheel
Hexanuclear and Tetranuclear Titanium Organophosphonates
Formed via a Common Single-4-Ring Intermediate: Insights into
Formation Pathways
Structural Characterization and Luminescence Studies of Au(I)
Complexes with PNP and PNB Based Ligand Systems
A Bimetallic Phosphorous-Based Complex as a Building Block
to Form Organometallic-Organic Hybrid Materials
Synthesis, crystal structure and properties of ferrocenyl based
pyridyl functionalized dithiocarbamate complexes of group 12
metals
Ligand Protected Zinc Clusters
Zinc-Zinc Interactions in Zinc Containing Complexes and
Clusters
Two Alternative Approaches to Access Mixed Hydride-Amido
Zinc Complexes: Synthetic, Structural and Solution Implications
Investigations on selenidozincates and –cadmates in ionic liquids
Bottom-Up! Intermetallic Nickel Gallium Molecular Clusters
and Complexes as Potential Precursors for Intermetallic
Nanoparticles
Incorporation of Small Molecules in Fullerene-like
Supramolecules
Rational molecular design: common-sense chemistry
New ionic liquids containing the 2-Phosphaethynolate-anion
Generation of a tripodal Schiff-base metalloligand
Preparation of Conducting Pani Graft Polymers
Methanol Synthesis in Silico.Quantumchmical Calculations on a
Cu4Zn3O3 Picomodel
Low valent Pentaaryl Cyclopentadienyl Fe, Co and Ni
Complexes
Reactions and characteristics of a cationic Ni(I)-Complex
The reactivity of [(C10H15)Fe(η5-P5)] and [(C5H2tBu3)Ni(η3-P3)]
Dinuclear Iron and Ruthenium Complexes Containing
Naphthalene as a Bridging Ligand
Transformations of Small Inorganic Molecules by Low-valent
Transition Metalate Anions and Transition Metal Radicals
Poster Contributions
Poster no
P158
Presenter
Sandra Hitzel
P159
Iwao Omae
P160
Ulrike Kroesen
P161
P162
P163
Philipp
Büschelberger
Dominik Naglav
Heiko Bauer
P164
Jürgen Pahl
P165
Laia Davin
P166
Lisa Vondung
P167
Michal Horni
P168
P169
P170
Mathies Evers
María Fernández
Millán
Dietmar Glindemann
P171
Johannes Schläfer
P172
Corinna Hegemann
P173
P174
Tim Heidemann
Aida Jamil
P175
Elif Okutan
Title of the Abstract
Coordination chemistry of new di-/monoanionic ferrocene-based
di-/phosphido chelate ligands
Applications of the five-membered ring products of
cyclometalation reactions as OLEDs
Carbolithiation vs. Deprotonation: Control of the Reaction
Behavior of Allylamines towards Alkyllithium Reagents
Polyarene Metalates as Precatalysts for Hydrogenations: Scope
and Mechanism
Studies on heteroleptic Cp*Be-R compounds
Calcium Hydride Catalyzed Highly 1,2-Selective Pyridine
Hydrosilylation
Synthesis and reactivity of an unprecedented cationic Mg βdiketiminate complex
Regioselective deprotonation of N-heterocyclic molecules using
ß-diketiminate stabilized magnesium bases
Towards new concepts for bond activation using an iron-PBPpincer complex
Trigonal to tetrahedral transitions in Cu(I) six-membered
inorganic true heterocycles
The Transmetalation Strategy to Heterometallic Gold Clusters
Chiral Potassium Derivatives bearing Ligands of Natural Origin
PTFE (“Teflon”) Sealing Ring for greaseless conical Glass Joint
and for All-Glass-Syringe
Synthesis of Functional Inorganic Materials starting from Metal
Alkoxide and Metal Thiolate Precursors
Precursor Synthesis for the Generation of Fluorine-dope SnO2
Nanomaterials
Exploring the Chemistry of Ternary Heterometallic Alkoxides
Ligand-Modulated Chemical and Structural Implications in
Aluminum Heteroaryl Alkenolates
BODIPY-Cyclophosphazene-Fullerene Triad as Heavy Atom
Free Organic Triplet Photosensitizer
Poster Contributions
Plenary
Lectures
Template Ring Approaches to Metallation Chemistry
Robert E. Mulvey
r.e.mulvey@strath.ac.uk
Pure & Applied Chemistry, University of Strathclyde
295 Cathedral Street, Glasgow G1 1XL, Scotland, UK
An indispensable tool in every synthetic chemist’s toolbox, metallation is used
routinely in academia and industry to transform inert, synthetically intractable C-H
bonds into reactive, synthetically tractable C-metal bonds. The seminal concept to
date in the metallation of aromatic compounds has been directed ortho-metallation,[1]
which is controlled predominately by the electron-accepting or -donating properties of
the substituent coupled with its Lewis basicity. This presentation will demonstrate that
mixed-metal ligand template structures[2] can be built that operating through special
synergistic effects between their various components can perform metallation
reactions outside the scope of conventional organolithium or lithium amide bases.
Fitting perfectly with the theme of IRIS, examples are given of inorganic (mixedmetal amide) ring structures (so called pre-inverse-crowns[3]) that act as templates for
deprotonation reactions unique in reactivity and selectivity, leading in the best cases
to products (inverse crowns) in which ortho-metallation effects of substituents have
been overridden by the template structure of the base.
Figure 1. Template base structure of a potassium-magnesium alkyl-amido pre-inverse-crown.
Acknowledgements: UK EPSRC and the Royal Society (Wolfson Merit Award) are thanked for their
generous sponsorship.
References:
[1] M. C. Whisler, S. MacNeil, V. Snieckus, P. Beak, Angew. Chem. Int. Ed. 2004, 43, 2206.
[2] A. J. Martínez-Martínez, A. R. Kennedy, R. E. Mulvey, C T. O ’Hara, Science 2014, 346, 834.
[3] D. R. Armstrong, B. Conway, B. J. Fleming, J. Klett, A. J. Martínez-Martínez, A. R. Kennedy, R.
E. Mulvey, S. D. Robertson, C T. O’Hara, Chem. Sci. 2014, 5, 771.
Plenary lecture - PL01
Evolving the Coordination Chemistry of p-Block Element Lewis
Acceptors
Neil Burford*, Saurabh S. Chitnis, Paul A. Gray and Alasdair P.M. Robertson
nburford@uvic.ca
Department of Chemmistry
University of Victoria, P.O. Box 3065, Stn CSC, Victoria, British Columbia, V8W
3V6, Canada
We have recently demonstrated that homoatomic coordination chemistry offers a
versatile approach to P-P bond formation, and a variety of synthetic methods are now
available. Extrapolation of coordination chemistry to other p-Block element acceptor
centers provides new approaches for general non-metal element-element bond
formation. More importantly, in the context of the coordination chemistry of the
transition metals, a potentially diverse and extensive coordination chemistry for nonmetal element acceptors is emerging for the tetraels (E = Si, Ge, Sn) and the
pnictogens (Pn = P, As, Sb, Bi), as illustrated (L = neutral ligand, X = halogen)
below. The synthesis, structure, bonding and reactivity for new complexes involving
non-metal acceptors with classical ligands will be described.
Figure 1. Coordination drawings.
Acknowledgements: Natural Sciences and Engineering Research Council of Canada for funding.
References:
Angew. Chem. Int. Ed., 2011, 50, 11474; 2012, 51, 2964; 2013, 52, 2042; 2013, 52, 4863; 2014, 53,
6050 (review); 2014, 53, 3480.
J. Am. Chem. Soc., 2014, 136, 12498; 2014, 136, 14941.
Chem. Commun., 2011, 47, 12331; 2012, 48, 7922; 2012, 48, 7359; 2014, 50, 7979.
Dalton, 2015, 44, 17 (review).
Chem. Sci., 2015, 6, 2559.
Plenary lecture - PL02
Phosphorus-Containing Ring Systems from Low to High Oxidation
States
Christopher C. Cummins
CCUMMINS@MIT.EDU
Massachusetts Institute of Technology
Cambridge, MA 02139
The book Nonexistent Compounds by W. E. Dasent gives consideration to
compounds "... whose structures do not offend the simpler rules of valence, but which
nevertheless are characterized by a low degree of stability." One such compound
mentioned in the book is the diatomic molecule P2. The presentation will delineate
synthetic access to sources of P2 that may be regarded (depending upon mechanism)
as thermal molecular precursors to P2 or as P2 transfer agents. Also to be described are
efforts to characterize volatilized species by molecular beam mass spectrometry and
by spectroscopy. Reactivity studies involving P2that lead to new inorganic ring
systems have been targeted, and these will be described with an eye to electronic
structure elucidation of the reaction products. Inorganic ring systems based on new
metaphosphate acid salt starting materials will be described as well, and here, an
emphasis is placed on understanding the ramifications and applications of weak-field
polyanions in coordination chemistry.
Plenary lecture - PL03
FLP-rings: Applications in Synthesis and Catalysis
Doug Stephan
dstephan@chem.utoronto.ca
Department of Chemistry, University of Toronto
80 St George St
Main group Lewis acids and bases are used in combination to activate hydrogen in
frustrated Lewis pairs (FLPs). This concept has allowed the development of metalfree routes to novel reactivity and catalysis. In this lecture, we will describe a number
of examples that demonstrate the utility of FLP-ring and Lewis acid systems in the
synthesis of novel reagents, materials, polymers and catalysts. For example, FLPrings systems have been used to stabilize the otherwise unstable molecule SO. New
approaches to Te-B electronic materials and polymers have been developed. In
addition, novel Lewis acid catalysts have been designed based on electrophilic
phosphorus based systems are discussed and shown to be effective for C-F bond
hydrodefluorination catalysis, hydrosilylations, and hydrogenations. The implications
of these findings for applications of main group species in materials chemistry and
catalysis is considered in this lecture.
Acknowledgements: NSERC of Canada
References:
L.E. Longobardi, V. Wolter, D.W. Stephan, Angew. Chem. Int. Ed. 2015,54, 809-812.
F.A. Tsao, D.W Stephan, Dalton Trans. 2015, 44 (1), 71-74.
F.A. Tsao, D.W Stephan, Chem. Commun. 2015,51, 4287–4289.
M.H. Holthausen, R.R. Hiranandani, D.W. Stephan, Chem. Sci. 2015, 6, 2016-2021.
J.M. Farrell, D.W. Stephan, Angew. Chem. Int. Ed. 2015, doi.org/10.1002/ange.201500198
Plenary lecture - PL04
New Phosphorus-Heterocycles from simple Building Blocks
Riccardo Suter, Dominikus Heift, Xiaodan Chen, Zoltan Benkö, Hansjörg
Grützmacher *
hgruetzmacher@ethz.ch
Department of Chemistry and Applied Biosciences
ETH Zurich Vladimir-Prelog-Weg 1 8093 Zürich Switzerland
Sodium phosphaethynolate is easily prepared from sodium, phosphorus, a tertiary
alcohol and a carbonate in a one-pot reaction.[1] It is best described by the resonance
structures -O-C≡P (A) and O=C=P- (B) and serves as building block for a variety of
phosphorus heterocycles with one, two, or three phosphorus centers (Figure 1).[2] In
some reactions, classical cycloadditions to the C≡P triple bond occur while in others
OCP- serves as a “P-” transfer reagent under loss of CO. Some of the newly prepared
heterocycles show remarkable properties such as strong absorptions in the visible
range of light. Furthermore, because all heterocycles obtained from OCP- are anionic,
they serve themselves as valuable building blocks for organophosphorus compounds
and transition metal complexes.[3] The syntheses of these species will be discussed
and some insight into the reaction mechanisms obtained from NMR spectroscopy on
intermediates combined with DFT computations will be given.
Figure 1: Various phosphorus heterocycles obtained from Na(OCP).
Acknowledgements: Funding by the ETH Zürich and Swiss National Science Foundation is gratefully
achnowledged
References:
[1] D. Heift, Z. Benkö, H. Grützmacher, Dalton Trans. 2014, 43, 5920-5928.
[2] D. Heift, Z. Benkö, H. Grützmacher, Chem. Eur. J. 2014, 20, 11326-11330.
[3] R. Suter, unpublished results.
Plenary lecture - PL05
Lewis Acidic Properties of Organoantimony Compounds:
Applications in Anion Sensing and Catalysis
François P. Gabbaï
francois@tamu.edu
Department of Chemistry, Texas A&M University
College Station, Texas 77843, USA
In this presentation, we will show that the oxidation of organo-antimony(III)
derivatives provides access to Lewis acidic antimony(V) derivatives which can be
used in a number of applications ranging from anion sensing to organic reaction
catalysis. The first part of the presentation will be dedicated to the chemistry of Lewis
basic bidendate distibines and their oxidative conversion into the corresponding
distiboranes.[1] These distiboranes behave as bidendate Lewis acids and readily
chelate anions such as the fluoride anion. In the second part of the presentation, we
will describe how stibines of general formula R3Sb can be oxidized even when ligated
to transition metal complexes (M). This oxidation induces the formation of a M→Sb
interaction which results in a drastic increase in the Lewis acidity of metal center.[2-4]
Using a family of gold stibine derivatives, we will demonstrate that such coordinated
stibine oxidation reactions can be used to afford potent hydroamination catalysts.
Figure 1. Example of a bidentate Lewis acidic fluoride receptor obtained by oxidation of the
corresponding distibine.
Acknowledgements: This work was supported by the National Science Foundation (CHE-1300371),
the Welch Foundation (A–1423) and Texas A&M University (Arthur E. Martell Chair of Chemistry)
References:
[1] M. Hirai, F. P. Gabbaï, Angew. Chem. Int. Ed. 2015, 54, 1205-1209.
[2] C. R. Wade, F. P. Gabbaï, Angew. Chem. Int. Ed. 2011, 50, 7369-7372.
[3] H. ang, T.-P. in, F. P. Gabba , Organometallics 2014, 33, 4368-4373.
[4] J. S. Jones, C. R. Wade, F. P. Gabbaï, Angew. Chem. Int. Ed. 2014, 53, 8876-8879.
Plenary lecture - PL06
Group-14 element rich cages and rings as precursors and
intermediates for the formation of intermetalloid clusters
Thomas F. Fässler
thomas.faessler@lrz.tum.de
Department of Chemistry
Lichtenbergstrasse 4, D-85747 Garching
Homoatomic frameworks, rings and cages frequently appear in intermetallic
compounds that are composed of p-block (semi)metals in combination with an
electropositive metal. Prominent examples of so-called Zintl phases are alkali-metal
tetrel phases that among others contain five membered Si5 rings, tetrahedral E4 units or
deltahedral E9 clusters (E = Si, Ge, Sn and Pb). Despite the fact that those Zintl phases
are known since a long time only a limited number is eligible for transferring these
units to soluble tetrel-rich molecular anions (Zintl anions). In recent years, however,
the chemistry of Zintl ions has emerged and developed to a fast-growing field and has
now provided a rich plethora of new compounds, including oxidative coupling
reactions leading to dimers, oligomers, or polymers, addition of organic ligands, or by
the inclu-sion of metal atoms under formation of endohedral (intermetalloid) cluster
species and many of them disclosing non-classical bonds . [1] Remarkably, the major
part of all reactions with organometallic precursors in solution reported so far involve
transition metal complexes with late d block metals (Group 6 to Group 12). We will
discuss recent results arising from our investigations into the reac-tivity of low-valent
tetrel compounds with early transition metals such as titanium.[2]
Figure 1. Examples of intermetalloids with an emphasis on three- or five-membered En rings.
References:
[1] a) S. Scharfe, F. Kraus, S. Stegmaier, A. Schier, T. F. Fässler, Angew. Chem. Int. Ed. 2011, 50,
3630; b) T. F. Fässler (Ed.), Zintl Ions: Principles and Recent Developments, Structure and Bonding,
Springer-Verlag: Heidelberg, 2011; c) M. M. Bentlohner, W. Klein, Z. H. Fard, L.-A. Jantke, T. F.
Fässler, Angew. Chem. Int. Ed. 2015, DOI: 10.1002/anie.201410199; d) M. Waibel, F. Kraus, S.
Scharfe, T. F. Fässler, Angew. Chem. Int. Ed. 2010, 49, 6611; e) J.-Q. Wang, S. Stegmaier, B. Wahl, T.
F. Fässler, Chem. Eur. J. 2010, 16, 1793; f) L. Yong, S .D. Hoffmann, T. F. Fässler, S. Riedel, M.
Kaupp, Angew. Chem. Int. Ed. Engl. 2005, 44, 2092.
[2] C. B. Benda, M. Waibel, T. F. Fässler, Angew. Chem. Int. Ed. 2015, 54, 522.
Plenary lecture - PL07
Novel approaches to E-H bond activation and functionalization using
Main Group systems
Simon Aldridge
Simon.Aldridge@chem.ox.ac.uk
Department of Chemistry, Oxford University
Inorganic Chemistry Laboratory, South ParksRoad, Oxford, OX1 3QR, UK
E-H bond activation processes represent key mechanistic steps in numerous catalytic
reactions of key industrial importance. Classically such activation is brought about via
oxidative addition utilizing the readily accessible n/n+2 redox states of ‘noble’
transition metals. Of late, economic and environmental imperatives have driven the
development of alternative catalysts, including systems based on either (i) cooperative
metal/ligand activation processes; and/or (ii) redox processes at a single (non-noble)
metal site. In recent work we have been examining both approaches, and present
recent results involving the activation and functionalization of H-H and N-H bonds.1,2
In terms of cooperative reactivity, ambiphilic systems capable of the activation of
protic, hydridic and apolar H-X bonds across a Group 13 metal/activated bdiketiminato (Nacnac) ligand framework have been developed. Related hydride
complexes derived from the activation of H2 can be shown to be competent catalysts
for the highly selective reduction of CO2 to a methanol derivative.1 In terms of redox
chemistry, bond modifying processes have been developed for group 14 metals. The
oxidative addition of H2 as well as both protic and hydridic E-H bonds (N-H/O-H, SiH/B-H, respectively) to Sn(II) can be driven by employing strongly s-donating boryl
ancillary ligands. In the case of ammonia and water, E-H oxidative addition can be
shown to be followed by reductive elimination to give an N- (or O-) borylated
product. Thus, in stoichiometric fashion at least, redox-based bond
cleavage/formation is demonstrated for a single Main Group metal centre.
Figure 1. Oxidative addition and reductive elimination at Sn(II).
Acknowledgements: EPSRC (grants EP/L025000/1 and EP/K014714/1).
References:
1. J.A.B. Abdalla, I.M. Riddlestone, R. Tirfoin, S Aldridge, Angew. Chem., Int. Ed., 2015, in press.
DOI: 10.1002/anie.201500570.
2. A.V. Protchenko, J.I. Bates, L. Saleh, M.P. Blake, A.D. Schwarz, E. Kolychev, A.L. Thompson, C.
Jones, P. Mountford, S. Aldridge, submitted.
Plenary lecture - PL08
Keynote
Lectures
Cyclic and Acyclic Boron-based Chromophores: Highly Unusual
Donor-Acceptor Systems
Holger Braunschweig
holger.braunschweig@uni-wuerzburg.de
University of Würzburg
Am Hubland D-97074 Würzburg
The incorporation of boron-based chromophores – most commonly electron-deficient
acceptor (A) units – into p-conjugated systems, has spurred significant interest over
the past 15 years due to the potential of such systems for applications in organic
electronics. We have contributed a variety of boron-based heterocycles – that is
aromatic borirenes and azaborinines as well as antiaromatic boroles – as cyclic
building blocks for extended π-conjugated systems. More recently we have also
developed a series of unprecedented electron-rich boron-based chromophores based
on B-B double and triple bonds. Here, new synthetic approaches – both stoichiometric
and catalytic - to such systems will be presented together with a survey of the highly
unusual electronic and photophysical properties of particularly substituted diborenes.
Acknowledgements: We thank DFG and ERC for financial support
References:
[1] P. Bissinger, A. Steffen, A. Vargas, R. D. D. Dewhurst, A. Damme, H. Braunschweig Angew.
Chem. 2015, 127, DOI: 10.1002/anie.201408993.
[2] P. Bissinger, H. Braunschweig, A. Damme, C. Hörl, I. Krummenacher, T. Kupfer Angew. Chem.
Int. Ed. 2015, 54, 359–362.
[3] H. Braunschweig, M. A. Celik, F. Hupp, I. Krummenacher, L. Mailänder Angew. Chem. Int. Ed.
2015, 54, accepted.
[4] H. Braunschweig, K. Geetharani, J. O. C. Jimenez-Halla, M. Schäfer Angew. Chem. Int. Ed. 2014,
53, 3500–3504.
[5] J. Böhnke, H. Braunschweig, P. Constantinidis, T. Dellermann, W. C. Ewing, I. Fischer, K.
Hammond, F. Hupp, J. Mies, H.-C. Schmitt, A. Vargas J. Am. Chem. Soc. 2015, 137, 1766–1769.
[6] H. Braunschweig, R. D. Dewhurst, K. Hammond, J. Mies, A. Vargas, K. Radacki Science 2012,
336, 1420–1422.
Keynote lecture - KL01
Activation of Small Molecules by Biradicaloids
Axel Schulz
axel.schulz@uni-rostock.de
Institut für Chemie, Universität Rostock
Albert-Einstein-Str. 3a, 18059 Rostock, Germany
This lecture deals with the synthesis and full characterization of biradicaloids of the
type [E(m-NTer)]2 (E = element of group 15, Scheme 1 species 2).[1-3] The reactivity
of these biradicaloids 2 was employed to activate small molecules bearing single,
double and triple bonds (Scheme 1). Addition of chalcogens (O2 , S8 , Sex and Tex ) led
to the formation of dichalcogen bridged E2N2 heterocycles. In formal [2πe+2πe]
addition reactions small unsaturated compounds such as ethylene, acetylene, acetone,
acetonitrile, tolane, diphenylcarbodiimide, and bis(trimethylsilyl)sulfurdiimide are
readily added to the E2N2 heterocycle of the biradicaloid 2 yielding novel
heteroatomic cage compounds. The reaction with CO and isonitriles led to the
formation of new cyclic 5-membered heterocycles featuring also biradical character.
Oxidation with silver salts gave stable cyclic radical cations (3+).
Scheme 1. Activation of small molecules by biradicaloids.
References:
[1] A. Hinz, R. Kuzora, A. Schulz, A. Villinger, Chem. Eur. J. 2014, 20, 14659 – 16673.
[2] A. Hinz, A. Schulz, A. Villinger, Angew. Chem. Int. Ed. 2015, 54, 668 – 672.
[3] A. Hinz, A. Schulz, A. Villinger, Angew. Chem. Int. Ed. 2015, 54, 2776 – 2779.
Keynote lecture - KL02
Boron-Cations and Radicals Stabilized by Strong P→B Interactions
M. Devillard, A. Rosenthal, G. Bouhadir, D. Bourissou
dbouriss@chimie.ups-tlse.fr
Laboratoire Hétérochimie Fondamentale et Appliquée
Paul Sabatier University, 118 route de Narbonne, 31062 Toulouse, France
Our group is interested in cooperative phenomena arising from ambiphilic
compounds. In this presentation, our recent studies on naphthyl-bridged phosphorusboron derivatives will be presented. The three following sub-topics will be discussed:
- Phosphine-boranes featuring strong, yet Lewis acid-responsive P→B interactions,[1]
- Phosphine-stabilized borenium salts featuring versatile reactivity,[2]
- Phosphine-stabilized boryl radicals: their electronic structure and chemical behavior.
Figure 1. Schematic representation of the naphthyl-bridged P/B derivatives
Acknowledgements: The CNRS, the Université Paul Sabatier and the Agence Nationale de la
Recherche are acknowledged for financial support of this work. We thank Dr. K. Miqueu (Université
de Pau et des Pays de l’Adour) for DFT calculations.
References:
[1] Bontemps, S.; Devillard, M.; Mallet-Ladeira, S.; Bouhadir, G.; Miqueu, K.; Bourissou, D. Inorg.
Chem. 2013, 52, 4714.
[2] Devillard, M.; Mallet-Ladeira, S.; Miqueu, K.; Bouhadir, G.; Bourissou, D. Angew. Chem. Int. Ed.
2015, DOI: 10.1002/anie.201500959.
Keynote lecture - KL03
New main group-metal-mediated strategies for ring functionalisation
Eva Hevia
eva.hevia@strath.ac.uk
WestCHEM, Department of Pure and Applied Chemistry,
University of Strathclyde, 295 Cathedral Street, G1 1XL, Glasgow, UK
Recent advances have established that cooperative characteristics can be instilled into
main group bimetallic systems by combining two different metals with distinct bond
polarities within the same compound. The outcome of this cooperativity is that the
bimetallic is capable of delivering new chemistry irreproducible by either of its
single-metal components. Despite many synthetic organic studies having utilised
these reagents, the key factors governing their reactions and cooperative behaviour
still remain to be elucidated and fully understood.[1] To complement these organicfocused studies and gain a better understanding of this intriguing area, we have
approached it from an alternative inorganic/structural/metal perspective. This
presentation will highlight our recent results that provide valuable insights into the
often blurred identities of the organometallic intermediates involved in key reactions
such as deprotonation,[2] metal-halogen exchange and Pd-catalysed cross-coupling .[3]
The first catalytic applications of these multicomponent reagents will also be
discussed focussing on hydroamination reactions of unsaturated organic molecules
such as isocyanates and olefins.[4] The opening applications of mixed ammoniummagnesiate salts in Green Chemistry will also be revealed through addition reactions
of Grignard reagents to ketones under air and at room temperature using Deep
Eutectic Solvents.[5]
References:
[1] F. Mongin, A. Harrison-Marchand, Chem. Rev. 2013, 113, 7563.
[2] (a) S. E. Baillie, T. D. Bluemke, W. Clegg, A. R. Kennedy, J. Klett, L. Russo, M. de Tullio, E.
Hevia Chem. Commun. 2014, 50, 12859. (b) D. R. Armstrong, S. E. Baillie, V. L. Blair, N. G. Chabloz,
J. Diez, J. Garcia-Alvarez, A. R. Kennedy, S. D. Robertson, E. Hevia, Chem. Sci. 2013, 4, 4259.
[3] T. D. Bluemke, W. Clegg, P. García-Alvarez, A. R. Kennedy, K. Koszinowski, M. D. McCall, L.
Russo, E. Hevia, Chem. Sci., 2014, 5, 3552.
[4] A. Hernán-Gómez, T. D. Bradley, A. R. Kennedy, Z. L. Livingstone, S. D. Robertson, E. Hevia,
Chem. Commun. 2013, 49, 8659.
[5] C. Vidal, J. Garcia-Alvarez, A. Hernan-Gomez, A. R. Kennedy, E. Hevia, Angew. Chem. Int. Ed.
2014, 53, 5969
Keynote lecture - KL04
Nucleophilic boron derivatives, stable phosphinidenes and other
main group species
Guy Bertrand
guybertrand@ucsd.edu
UCSD/CNRS Joint Research Chemistry Laboratory
University of California San Diego, La Jolla, CA, 92093-0343
In the first part of the lecture we will present results dealing with the preparation and
reactivity of neutral and anionic boron derivatives.1 Then we will show that
electrophilic carbenes, such as cyclic (alkyl)(amino)carbenes and pyramidalized
NHCs can stabilize a variety of main group species in different oxidation states.2 The
last part of the lecture will be devoted to the synthesis, reactivity and coordination
behavior of the first stable phosphino nitrenes (nitrido-phosphorus)3 and
phosphinidenes.4
References:
1 D. A. Ruiz, G. Ung, M. Melaimi, G. Bertrand, Angew. Chem. Int. Ed. 2013, 52, 7590-7592.
2 R. Kretschmer, D. A. Ruiz, C. E. Moore, A. L. Rheingold, G. Bertrand, Angew. Chem. Int. Ed. 2014,
53, 8176-8179.
3 F. Dielmann, D. M. Andrada, G. Frenking, G. Bertrand,J. Am. Chem. Soc. 2014, 136, 3800-3802.
4 L. Liu, D. Ruiz, G. Bertrand, Unpublished results
Keynote lecture - KL05
Base-Induced Isomerization of Unsaturated Group 14 Ring Systems
Michael J. Cowley, Anukul Jana, David Nieder, Kai Abersfelder, and David
Scheschkewitz*
scheschkewitz@mx.uni-saarland.de
Krupp-Chair of General and Inorganic Chemistry, Saarland University
D-66125 S
The coordination of Lewis bases to unsaturated main group systems exerts a
considerable stabilising effect. Various otherwise inaccessible structural motifs have
been isolated as stable adducts with N-heterocyclic or cyclic alkyl amino carbenes.[1]
The nature of this interaction is subject of an ongoing discussion, in particular with
regards to the alternative descriptions of the bonding situation as either donoracceptor bond or ylidic charge-separated systems.[2] We argued that reversibility of
coordination is at least a sufficient criterion for the presence of a donor-acceptor
interaction.[3] The lecture will discuss our recent results regarding the interaction of
unsaturated Group 14 ring systems with N-heterocyclic carbenes and silylenes in this
light, with a focus on base-coordinated stable representatives of the Si2(EX)R3
manifold (Scheme 1, EX = SiR,[4] GeCl,[5] P, GePh, etc.; R = Tip = 2,4,6-iPr3C6H2).
Isomerization pathways include ring closure and opening, as well as 1,2- and 1,3migration of functional groups. Exchange and sequestration reactions of Nheterocyclic carbenes under mild conditions support the notion of reversibility. Subtle
changes in size and/or donor properties of the coordinated base allow for the isolation
of various unsaturated isomers with often dramatically altered physical properties. In
selected cases coordinated and uncoordinated species in solution even co-exist in
equilibrium providing firm support for weak donor-acceptor interactions in these
cases. The potential of the newly emerging toolbox of synthetic manipulations for the
construction of extended systems in lowvalent main group chemistry will be
discussed.
References:
[1] Review: Y. Wang, G. H. Robinson, Inorg. Chem. 2014, 53, 11815.
[2] (a) D. Himmel, I. Krossing, A. Schnepf, Angew. Chem. Int. Ed. 2014, 53, 370. (b) G. Frenking,
Angew. Chem. Int. Ed. 2014, 53, 6040. (c) R. Köppe, H. Schnöckel, Chem. Sci. 2015, 6, 1199.
[3] (a) A. Jana, V. Huch, H. S: Rzepa, D. Scheschkewitz, Angew. Chem. Int. Ed. 2015, 54, 289–292.
(b) A. Jana, V. Huch, H. S. Rzepa, D. Scheschkewitz, Organometallics 2015, DOI:
10.1021/om501286g.
[4] M. J. Cowley, V. Huch, H. S. Rzepa, D. Scheschkewitz, Nat. Chem. 2013, 5, 876.
[5] A. Jana, V. Huch, D. Scheschkewitz, Angew. Chem. Int. Ed. 2013, 52, 12179.
Keynote lecture - KL06
Low oxidation state main group compounds: stabilisation strategies
and transition metal-like reactivity
Cameron Jones
cameron.jones@monash.edu
School of Chemistry, Monash University
PO Box 23, Melbourne, VIC, 3800, Australia
Considerable progress has been made over the last decade towards the stabilisation of
very low oxidation state p-block compounds with bulky ligands. In this lecture the
development of a new class of extremely bulky monodentate amido ligands will be
discussed, as will their use in the preparation of previously inaccessible,
coordinatively unsaturated low oxidation state p-block metal complex types.[1] The
facile "transition metal-like" reactivity of these compounds towards small molecule
(e.g. H2, CO2, NH3 etc.) activations, and associated catalytic processes, will also be
detailed.[2]
Acknowledgements: Australian Research Council, US Air Force
References:
1. T.J. Hadlington, M. Hermann, J. Li, G. Frenking, C. Jones, Angew. Chem. Int. Ed., 2013, 52, 10199
2. T.J. Hadlington, M. Hermann, G. Frenking, C. Jones, C. J. Am. Chem. Soc. 2014, 136, 3028.
Keynote lecture - KL07
Boron Cations and Poly-dentate Divalent Group 14 Ligands
Ching-Wen Chiu
cwchiu@ntu.edu.tw
Department of Chemistry, National Taiwan University
No. 1, Sec. 4, Roosevelt Rd., Taipei, 10617, Taiwan
Studies on organoboranes have shown that the introduction of positive charge at
boron center greatly enhances the electron deficiency of the molecule. Although
boron mono-cations have proved to be effective in Lewis acid promoted organic
transformations, reactivity studies of boron poly-cations remain relatively limited.
Recently, our group has shown that [η5-Cp*B-IMes]2+, a di-substituted boron
dication, could be transformed into the corresponding carbene-stabilized borabenzene
upon addition of superhydride.[1] To gain better insight into boron dication, a series of
closely related boron mono- and di-cations are synthesized. Reactivity and electron
deficiency of these boron cations will also be addressed. In addition to boron cations,
our group are also interested in bridging type poly-dentate N-heterocyclic carbenes
and metallylenes. To this end, we have achieved the isolation of multi-dentate NHC
ligands via stepwise synthesis or through assembly process.[2] In addition, a series of
triphenylene-based planar tritopic metallylene, including germylenes, stannylenes and
plumbylenes, are prepared. Theoretical computation on the aggregation induced color
change of N-phenyl tris-germylene is also discussed.
Acknowledgements: Ministry of Science and Technology of Taiwan
References:
[1] C.-T. Shen, Y.-H. Liu, S.-M. Peng, C.-W. Chiu, Angew. Chem. Int. Ed., 2013, 52, 13293.
[2] (a) Y.-T. Wang, M.-T. Chang, G.-H. Lee, S.-M. Peng, C.-W. Chiu, Chem. Commun., 2013, 49,
7258; (b) J.-H. Su, G.-H. Lee, S.-M. Peng, C.-W. Chiu, Dalton Trans., 2014, 43, 3059; (c) Y.-H. Chen,
K.-E. Peng, G.-H. Lee, S.-M. Peng, C.-W. Chiu, RSC Adv.,2014, 4, 62789.
Keynote lecture - KL08
From Metalloaromaticity to N-Heterocyclic Carbenes: The Evolution
of Inorganic Rings
Gregory H. Robinson*
robinson@uga.edu
Department of Chemistry, The University of Georgia
Athens, Georgia 30602 USA
Two decades ago we reported a compound containing a ring of three gallium atoms,
Na2[GaR]3.[1] This organometallic compound, a 2π-electron system isoelectronic with
the aromatic triphenylcyclopropenium cation, offered experimental realization of
metalloaromaticity - the concept that a metallic ring system could exhibit traditional
aromatic behavior. Recently, we initiated an effort to explore the main group
chemistry of N-heterocyclic carbenes, and have prepared a number of interesting
carbene-stabilized compounds - some of which contain novel three-membered rings
such as P2B [2] and Si2O (below). Indeed, the recently reported compound containing
the Si2O ring is a rare molecular example of a stabilized silicon oxide moiety. This
talk will concern our most recent results in the synthesis of inorganic ring systems and
place them in historical perspective with our earlier work.
References:
[1] X.-W. Li., W. T. Pennington, G. H. Robinson J. Am. Chem. Soc., 1995, 117, 7578.
[2] Y. Wang, Y. Xie, M. Y. Abraham, P. Wei, H. F. Schaefer III, P. v. R. Schleyer, G. H. Robinson
Chem.Comm., 2011, 47, 9224.
Keynote lecture - KL09
Catalysis in Service of Main Group Chemistry: Metal-Mediated and
Metal-Free Routes to Molecules and Materials based on Elements
from Group 13-15
Ian Manners
ian.manners@bristol.ac.uk
School of Chemistry, University of Bristol
Cantock's Close, Bristol, BS8 1TS, UK
Although metal-catalyzed reactions have played a profound role in organic synthesis,
catalytic routes to main group molecules and materials are much less explored.1 In
this talk the use of catalytic processes to dehydrogenate group 13 – 15 Lewis acidLewis base adducts such as amine- and phosphine-boranes and related species will be
discussed. In addition to mechanistic details, unexpected discoveries such as metalfree hydrogen exchange reactions will be described. The work has relevance to the
synthesis of new polymeric (e.g. polyamino- and phosphinoboranes, analogs of
polyolefins with a BN/BP backbone) and 2D materials and also to hydrogen storage
and transfer chemistry. 2
References:
1. Leitao, E.M.; Jurca, T.; Manners, I. Nature Chem. 2013, 5, 857.
2. Schaefer, A.; Jurca, T. et al Angew. Chem. Int. Ed. 2015 in press.
Keynote lecture - KL10
Inorganic Heterocycles: From Light-emitting Entities to Surprising
Products from Ligand Activation
Eric Rivard, Gang He, Melanie W. Lui, William Torres Delgado, Olena Shynkaruk,
S. M. Ibrahim Al-Rafia
erivard@ualberta.ca
Department of Chemistry, University of Alberta
11227 Saskatchewan Dr., Edmonton, Alberta, Canada, T6G 2G2
Our group has had a long standing interest in inorganic ring systems [1] with particular
recent focus given to the development of tellurophenes which show rarely observed
phosphorescence in the solid state in the presence of oxygen.[2,3] In addition, during
our explorations of N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins
(NHOs) as donors to main group element species [4], we uncovered unusual ringexpansion/ligand activation processes involving these generally thought to be inert
Lewis bases [5,6].
Acknowledgements: This research was supported by NSERC of Canada, Alberta InnovatesTechnology Futures and the Canada Foundation for Innovation
References:
[1] G. He, O. Shynkaruk, M. W. Lui, E. Rivard, Chem. Rev. 2014, 114, 7815.
[2] G. He, E. Rivard et al. Angew. Chem., Int. Ed. 2014, 53, 4587.
[3] G. He, E. Rivard et al. Chem. Commun. 2015, 51, 5444.
[4] E. Rivard, Dalton Trans. 2014, 43, 8577 and references therein.
[5] S. M. I. Al-Rafia, R. McDonald, M. J. Ferguson, E. Rivard, Chem. Eur. J. 2012, 18, 13810.
[6] M. W. Lui, C. Merten, M. J. Ferguson, R. McDonald, Y. Xu, E. Rivard, Inorg. Chem. 2015, 54,
2040.
Keynote lecture - KL11
Main Group Strategy for Photo and Electronic Functions
Shigehiro Yamaguchi
yamaguchi@chem.nagoya-u.ac.jp
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University,
Furo, Chikusa, Nagoya, 464-8602, Japan
Incorporation of main group elements into -conjugated skeletons is a powerful
strategy to develop new photo- or electro-functional molecules with unusual
properties. Representative design principles are to make use of an orbital interaction
between a  skeleton and a main group element moiety, or to utilize the coordination
number change of a main group element. Based on these approaches, we have so far
developed various types of electronic and sensory materials. In this lecture, we would
like to discuss recent progress in our chemistry regarding the following two subjects.
First, we have recently succeeded in the preparation of a series of model compounds
for boron-doped graphenes, such as compound 1.[1] These compounds were obtained
as a stable compound due to the structural constraint in an enforced planar fashion.[2]
The detailed studies on their reactivity and properties demonstrate the potential
utilities for this material class.[3] Second, we have also developed phosphoruscontaining fluorescence probes for bioimaging.[4] Incorporation of an electronwithdrawing phosphine oxide moiety into a -skeleton enables us to produce highly
electron-accepting scaffolds, such as a phosphole P-oxide, which were employed by
the combination with electron-donating groups to produce environment-sensitive
fluorescent probes like 2.
References:
[1] a) S. Saito, K. Matsuo, S. Yamaguchi, J. Am. Chem. Soc. 2012, 134, 9130. b) C. Dou, S. Saito, K.
Matsuo, I. Hisaki, S. Yamaguchi, Angew. Chem. Int. Ed. 2012, 51, 12206. c) K. Matsuo, S. Saito, S.
Yamaguchi, J. Am. Chem. Soc. 2014, 136, 12580.
[2] Z. Zhou, A. Wakamiya, T. Kushida, S. Yamaguchi, J. Am. Chem. Soc. 2012, 134, 4529.
[3] T. Kushida, A. Shuto, M. Yoshio, T. Kato, S. Yamaguchi, Angew. Chem. Int. Ed. 2015, in press.
[4] E. Yamaguchi, C. Wang, A. Fukazawa, M. Taki, Y. Sato, T. Sasaki, M. Ueda, N. Sasaki, T.
Higashiyama, S. Yamaguchi, Angew. Chem. Int. Ed. 2015, in press.
Keynote lecture - KL12
Ligand-Based Redox Chemistry with Aluminum(III)
Louise A. Berben
laberben@ucdavis.edu
Department of Chemistry, University of California
1 Shields Ave, Davis, CA 95616
This talk will describe the synthesis and characterization of a series of Al(III)
complexes which are stabilized by iminopyridine-based ligands. As an example, I will
describe the structure and reactivity of (PhI2P)AlCl and (PhI2P)AlH which both have
square planar geometry around the aluminum center (PhI2P is a phenyl substituted
tridentate bis(imino)pyridine ligand). The Al centers in these square planar molecules
are Lewis acidic and coordinate bases such as phosphines, pyridine, and ethers to
become five-coordinate. In the presence of weak acids such as alcohols (or amines),
O-H (or N-H) bond activation is observed where the proton is transferred to the amido
donor atom of the PhI2P ligand. The activation of these polar bonds leads to
dehydrogenation of the substrates in the examples where the substrate has a beta C-H
bond. In addition to this metal-ligand cooperative proton transfer chemistry, we have
also explored ligand-based proton and electron transfer chemistry. Using (PhI2P)AlCl,
the ligand can be protonated twice, and then reduced by two electrons to
quantitatively generate H2 . Performed electrochemically, this reaction is catalytic in
production of H2 via the ligand-based proton and electron transfer events.
Keynote lecture - KL13
Novel phosphorus-containing ring systems derived from the 2phosphaethynolate anion
Jose M. Goicoechea*
jose.goicoechea@chem.ox.ac.uk
Department of Chemistry, University of Oxford
Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, U.K.
The 2-phosphaethynolate anion (PCO−), first reported by Becker and co-workers,[1]
can be readily accessed by carbonylation of the heptaphosphide trianion [P 7]3−.[2] This
heavier cyanate analogue contains a reactive P−C multiple bond and can be employed
as an ambidentate nucleophile or as a precursor to novel phosphorus-containing
compounds.[3] For example, [2+2] cycloaddition reactions with heteroallenes
(carbodiimides and isocyanates) give rise to four-membered rings containing a
phosphide vertex.[1] Similarly, PCO− reacts with molecules with unsaturated maingroup element–element bonds also affording novel heteroatomic ring systems.[4] By
analogy with Wöhler’s urea synthesis, direct reaction of PCO− with ammonium salts
has been shown to yield phosphinecarboxamide (PH2C(O)NH2 ; Scheme 1), an airand moisture-stable primary phosphine.[5] This talk will focus on recent developments
concerning the chemical reactivity of PCO− and PH2C(O)NH2 for the formation of
novel neutral and anionic inorganic ring systems.
Figure 1. Synthesis of phosphinecarboxamide.
Acknowledgements: We thank the University of Oxford and the EPSRC (EP/K039954/1) for financial
support.
References:
[1] G. Becker, W. Schwarz, N. Seidler, M. Westerhausen, Z. Anorg. Allg. Chem., 1992, 612, 72.
[2] A. R. Jupp, J. M. Goicoechea, Angew. Chem., Int. Ed., 2013, 52, 10064.
[3] See for example: (a) S. Alidori, D. Heift, G. Santiso-Quinones, Z. Benkő, H. Grützmacher, M.
Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem.−Eur. J., 2012, 18, 1 0 (b) . Chen, S.
Alidori, F. F. Puschmann, G. Santiso-Quinones, Z. Benkő, Z. i, G. Becker, H.-F. Grützmacher, H.
Grützmacher, Angew. Chem. Int. Ed., 2014, 53, 1 1 (c) D. Heift, Z. Benkő, H. Grützmacher,
Angew. Chem. Int. Ed., 2014, 53, 7 7 (d) A. M. Tondreau, Z. Benkő, J. R. Harmer, H. Grützmacher,
Chem. Sci. 2014, 5, 1545.
[4] T. P. Robinson, M. J. Cowley, D. Scheschkewitz, J. M. Goicoechea, Angew. Chem., Int. Ed., 2015,
54, 683.
[5] A. R. Jupp, J. M. Goicoechea, J. Am. Chem. Soc., 2013, 135, 19131.
Keynote lecture - KL14
Early Main Group Metal Hydride Complexes
Sjoerd Harder*
Sjoerd.Harder@fau.de
Inorganic and Organometallic Chemistry, University Erlangen-Nürnberg
Egerlandstrasse 1, 91058 Erlangen, Germany
The enormous lattice energies for group 1 and 2 metal hydride salts, (MH)n and
(MH2)n, make the syntheses and isolation of well-defined early main group metal
hydride complexes a major challenge.[1] In here we present synthetic methods towards
such metal hydride complexes, their use in catalysis[2] and their role as molecular
models for hydrogen storage systems.[3]
References:
[1] S. Harder, Chem. Commun. 2012, 48, 11165.
[2] (a) S. Harder, Chem. Rev. 2010, 110, 3852. (b) A. G. M. Barrett, M. R. Crimmin, M.S. Hill, P. A.
Procopiou, Proc. R. Soc. A 2010, 466, 927. (c) M. R. Crimmin, M. S. Hill, Topics in Organometallic
Chemistry, Ed. S. Harder, 2013, 45, 191.
[3] (a) S. Harder, J. Spielmann, J. Intemann, H. Bandmann, Angew. Chem. Int. Ed. Engl. 2011, 50,
4156. (b) J. Intemann, J. Spielmann, S. Harder, Chem. Eur. J. 2013,19, 8478.
Keynote lecture - KL15
Bermuda-Clusters…? On the Interaction of Chelating Bipyridines
with Subvalent Gaand InSalts of the [Al(ORF)4]WCA.
Ingo Krossing*
krossing@uni-freiburg.de
Institute for Inorganic and Analytical Chemistry, University of Freiburg
Albertstr. 21, GER-79104, Freiburg
When Ag+[Al(ORF)4]– and metallic gallium or indium are sonicated in aromatic
solvents like fluorobenzene, a precipitate of silver metal and highly soluble
M(C6H5F)n+ salts (M = Ga, In; n = 2, 3) with the weakly coordinating [Al(ORF)4]–
anion are formed in a oxidative route in quantitative yield. These materials proved to
be valuable for coordination chemistry with a wide range of classical ligands like
phosphanes, crown ether, NHCs etc. By contrast, 2,2’‑bipyridine (bipy) triggers a
disproportionation of the univalent gallium salt [Ga(C6H5F)2]+[Al(ORF)4]– (RF =
C(CF3)3). In the resultant monomeric and paramagnetic [Ga(bipy)3]2+ complex, the
gallium cation is coordinated in a distorted octahedral fashion by three bipy ligands.
Excluding the formation of a gallium(II) species, the EPR and DFT investigations
clearly assign a ligand‑centered radical: i.e., a [GaIII(bipy)2(bipy)●−]2+ complex. The
application of the heavier homologue [In(C6H5F)2]+[Al(ORF)4]– astonishingly led to
aggregation and we isolated the first cationic, homonuclear, three‑ and four‑
membered triangular (Bermuda-?)clusters of univalent indium: [In3(bipy)6]3+,
[In3(bipy)5]3+ and [In4(bipy)6]4+ (Figure 1). Herein, the indium(I) cations are
coordinated by one, 1.5 or two bipy ligands in a chelating, trigonal or tetragonal
pyramidal fashion and form In−In bonded triangular and rhombic clusters. To our
knowledge, the In−In distances (2 .1−2 9. pm) include the shortest that have been
reported so far. DFT studies suggest a stepwise formation of the clusters, possibly via
their triplet state, and Born‑Haber‑Cycle investigations attribute the overall driving
force of the reactions to the high lattice enthalpies of the resultant MX3and MX4salts.
Figure 1. Molecular structures of Indium-bipyridine complexes, all balanced by the
[Al(ORF)4]- WCA.
Keynote lecture - KL16
New Aspects in the Chemistry of Al-containing Cyclic Compounds
Norihiro Tokitoh
tokitoh@boc.kuicr.kyoto-u.ac.jp
Institute for Chemical Research, Kyoto University
Gokasho, Uji, Kyoto 611-001, Japan
Group 13 element heteroles potentially exhibit unique properties originating from the
orbital interactions between the vacant p orbital of the group 13 elements and the π*
orbitals of the butadiene moieties.1 However, reports on heavier group 13 heteroles,
such as alumoles (1-alumacyclopenta-2,4-dienes), have been limited so far.2 Recently,
we have reported the synthesis of the first stable Lewis-base free alumole 1 by using
the bulky Mes* group (Mes* = 2,4,6-(t-Bu)3C6H2) (Scheme 1).3 In this presentation,
synthesis and properties of a new type of alumole derivative, 1-bromoalumole 2, will
be discussed.4 1-Bromoalumole 2 was obtained as a thermally-stable crystalline solid
by the treatment of 4,5-diethyl-3,6-dilithio-3,5-octadiene (3) with AlBr3. In the solid
state, 1-bromoalumole 2 forms a dimer owing to the coordination of the π(C=C) bond
of one molecule of 2 to the vacant 3p(Al) orbital of another molecule of 2. Reactions
of 2 with Mes*Li and LiN(SiMe3)2 afforded Mes*-substituted alumole 1 and 1aminoalumole–THF complex 4,5 respectively. Reactions of 2 with other reagents
including alkynes will also be reported.
Scheme 1
References:
[1] a) S. Yamaguchi, A. Wakamiya, Pure Appl. Chem. 2006, 78, 1413; b) H. Braunschweig, T. Kupfer,
Chem. Commun. 2011, 47, 10903.
[2] Important reports on alumoles: a) H. Hoberg, R. Kraus-Göing, J. Organomet. Chem. 1977, 127,
C29; b) C. Krüger, J. C. Sekutowski, H. Hoberg, R. Kause-Göing, J. Organomet. Chem. 1977, 141,
141; c) H. Hoberg, W. Richter, J. Organomet. Chem. 1980, 195, 347.
[3] T. Agou, T. Wasano, P. Jin, S. Nagase, N. Tokitoh, Angew. Chem. Int. Ed. 2013, 52, 10031.
[4] T. Wasano, T. Agou, T. Sasamori, N. Tokitoh, Chem. Commun. 2014, 50, 8148.
[5] T. Agou, T. Wasano, T. Sasamori, N. Tokitoh, Organometallics 2014, 33, 6963.
Keynote lecture - KL17
Oral
Presentations
Main Group Elements as Transition Metals: Reactions of
Phosphorus-Carbon Multiple Bonds with Small Molecules
Rosalyn L. Falconer, Christopher A. Russell*
Chris.Russell@bristol.ac.uk
School of Chemistry, University of Bristol
Cantock’s Close, Bristol, BS8 1TS, UK
One of the key goals of modern main group chemistry is to mimic reactivity most
commonly associated with the transition metals.[1] This challenge can be met by
utilising both HOMO and LUMO orbitals on the main group molecule, which, when
acting in concert, can lead to the activation of small molecules - this key concept
underpins much of the important reactivity and applications of d-block chemistry.
Several main group systems, for example, heavy p-block multiple bonds, Frustrated
Lewis Pairs and contemporary carbene chemistry, are celebrated for demonstrating
aspects of such reactivity. Herein we dicsuss the extension of this concept to
phosphorus-carbon multiple bonds.[2] We will explore the reactivity of some specific
examples of P/C multiple bonds in the activation of small molecules (for example, H2,
alkenes, dienes, silanes, germanes) from both a synthetic and mechanistic viewpoint.
Acknowledgements: We acknowledge the Bristol Synthetic Chemistry Doctoral Training Centre for
funding
References:
[1] P. P. Power, Nature 2010, 463, 171-177.
[2] a) N. S. Townsend, M. Green, C. A. Russell, Organometallics 2012, 31, 2543-2545; b) N. S.
Townsend, S. R. Shadbolt, M. Green, C. A. Russell, Angew. Chem. Int. Ed. 2013, 52, 3481-3484; c) L.
E. Longobardi, C. A. Russell, M. Green, N. S. Townsend, K. Wang, A. J. Holmes, S. B. Duckett, J. E.
McGrady, D. W. Stephan, J. Am. Chem. Soc. 2014, 136, 13453-13457.
Oral presentation - A01
The Addition-Isomerization Polymerization of Phosphaalkenes
Shuai Wang, Andrew Priegert, Spencer Serin, Derek P. Gates*
dgates@chem.ubc.ca
Department of Chemistry, University of British Columbia
2036 Main Mall, Vancouver, BC, Canada, V6T 1Z1
The addition polymerization of olefins is perhaps the most widely used and general
method for the preparation of commodity polymers. For the past decade, we have
been investigating the extension of addition polymerization to the P=C bond of
phosphaalkenes.1 In particular, we have reported that MesP=CPh2 may be
polymerized using thermal, radical or anionic methods of initiation. The resultant
polymers, poly(methylenephosphine)s (PMPs), represent a new class of functional
phosphorus-containing macromolecule. Recently, we have discovered that the radical
polymerization of MesP=CPh2 with alkoxyamine, Ph(Me)CH·TEMPO, follows an
unprecedented addition-isomerization mechanism.2 The addition step appears to be
followed by an unexpected H-atom transfer from the ortho-Me group of the Mes
substituent. Thus, the microstructure of PMP is better represented by (1, x > y). This
presentation will describe our latest mechanistic findings for the polymerization of
MesP=CPh2 and related derivatives. Of particular focus will be the study of the anioninitiated polymerization including the stepwise addition to the P=C bond and the
possibility of isomerization during the propagation. In addition, new directions in the
synthesis of functional phosphine-containing polymers such as PMPs will be
discussed.3
Acknowledgements: We thank NSERC of Canada for supporting this work.
References:
1 For a review, see : Bates, J. I.; Dugal-Tessier, J.; Gates, D. P. Dalton Trans. 2010, 39, 3151.
2 Siu, P. W. ; Serin, S. C.; Krummenacher, I.; Hey, T. W.; Gates, D. P. Angew. Chem. Int. Ed. 2013,
52, 6967.
3 Rawe, B. W.; Chun, C. P.; Gates, D. P. Chem. Sci. 2014, 5, 4928; S. C. Serin, B. O. Patrick, G. R.
Dake, D. P. Gates, Organometallics, 2014, 33, 7215.
Oral presentation - A02
Highly electron-rich phosphines for the activation of small molecules
Fabian Dielmann
dielmann@uni-muenster.de
Department of Inorganic and Analytical Chemistry, University of Münster
Corrensstrasse 30, GER-48149, Münster
Owing to their strong σ-donor properties N-heterocyclic carbenes play an important
role as ligands in transition metal catalysis as well as for the activation of small
molecules. As part of our program to enhance the donor strength of phosphines we
report a conceptually new approach based on the use of imidazol-2-ylidenamino
groups directly attached to the phosphorus atom. The new phosphines depict excellent
donor abilities, which can even exceed that of N-heterocyclic carbenes. Furthermore,
the steric and electronic properties of the new ligands can be easily varied owing to
the facile and modular synthesis. Our approach to highly electron-rich phosphines
provides new perspectives for the development of transition metal catalysts and for
the activation of small molecules.
Figure 1. Donor abilities of imidazol-2-ylidenaminophosphines
Oral presentation - A03
Synthesis and Reactivity of a Zwitterionic Diphosphanide
Kai Schwedtmann, Felix Hennersdorf, Michael H. Holthausen, Jan J. Weigand*
jan.weigand@tu-dresden.de
Department of Chemistry and Food Chemistry, Dresden University of Technology
Mommsenstrasse 4, GER-01062, Dresden
The cage compound [DippP5Cl][GaCl4][1] (Dipp = 2,6-diisopropylphenyl) reacts with
three equivalents of a NHC (N-heterocyclic carbene) via an unprecedented [3+2]fragmentation of the P5-core to give an imidazoliumyl-substituted P3+-cation and a
zwitterionic diphosphanide (see chart).[2] The structure of this unusual zwitterionic
diphosphanide is confirmed by NMR spectroscopy and X-ray diffraction analysis.
Subsequent transformation reactions of diphosphanides give access to new, interesting
phosphorus compounds such as imidazoliumyl-substituted cationic diphosphanes and
diphosphenes.
Acknowledgements: This work was supported by the Fonds der Chemischen Industrie (FCI, Liebig
scholarship for F.H. and M.H.H) and the German Science Foundation (DFG, WE 4621/2-1).
References:
[1] M. H. Holthausen, J. J. Weigand, Chem. Soc. Rev., 2014, 43, 6639 – 6657.
[2] M. H. Holthausen, S. K. Surmiak, P. Jerabek, G. Frenking, J. J. Weigand, Angew. Chem. Int. Ed.,
2013, 52, 11078 – 11082.
Oral presentation - A04
'Inorganic' Arylphosphines
Jonathan A. Bailey, Hazel A. Sparkes, Paul G. Pringle*
paul.pringle@bristol.ac.uk
School of Chemistry, University of Bristol
Cantocks Close, Bristol BS8 1TS, UK
Arylphosphines are a hugely important class of compounds whose applications in
synthetic chemistry range from stoichiometric organic synthesis to coordination
chemistry and homogeneous catalysis. We are interested in the synthesis of
arylphosphines in which C2 fragments of the aryl ring have been formally replaced
with isoelectronic BN fragments.[1] In this presentation, the preparation and chemistry
of borylphosphines of the type 1-3 shown in Figure 1 will be discussed. In particular,
the remarkably specific insertion of oxygen into the P-B bonds to give P-O-B systems
will be rationalised. Compounds 1-3 behave as electron-rich ligands to late transition
metals to give complexes with applications in homogeneous catalysis. Recently we
have succeeded in making triborazinylphosphine 3c or "inorganic
triphenylphosphine". Similarities and differences between the chemistry of 3c and
triphenylphosphine will be discussed.
Figure 1. Azaborinylphosphines: 'inorganic' analogues of arylphosphines.
Acknowledgements: We thank the European Union (Marie Curie ITN SusPhos, Grant Agreement No.
317404) for financial support.
References:
[1] (a) J. A. Bailey, H. A. Sparkes, P. G. Pringle, Chem. Eur. J., 2015, 21, 5360. (b) J. A. Bailey, M.
Ploeger, P. G. Pringle, Inorg. Chem., 2014, 53, 7763. (c) J. A. Bailey, M. F. Haddow, P. G. Pringle,
Chem. Commun., 2014, 50, 1432.
Oral presentation - A05
An Al/P Based Frustrated Lewis Pair as an Efficient Ambiphilic
Ligand for the Coordination and Activation of Polar Compounds
Philipp Wegener, Agnes Wollschläger, Werner Uhl*
uhlw@uni-muenster.de
Institut für Anorganische und Analytische Chemie, Universität Münster
Corrensstrasse 30, GER 48149 Münster
The Al/P based frustrated Lewis pair 1 is obtained by hydroalumination of the
corresponding alkynylphosphine.[1] It is an excellent starting compound for the
activation of various substrates and an efficient ambiphilic ligand for the coordination
of a wide variety of bifunctional atoms or molecules. The reaction with azides led to
the formation of adducts (2) which featured four-membered AlCPN heterocycles and
azide groups in terminal position. Heating of 2 resulted in release of nitrogen and the
formation of nitrene adducts 3 in which the electron sextet species nitrene is captured
by coordination to the Lewis basic phosphorus and Lewis acidic aluminium atoms.
Compound 4 represents the bifunctional stabilization of monomeric gallium hydride.
It has a mixed metal Ga-H-Al 3c-2e bond and was obtained by treatment of 1 with
GaH3×NMe2Et. Boron trihalides yielded adducts (5) with the boron atoms bonded to
phosphorus and one halogen atom in the bridging position between aluminum and
boron atoms. Rearrangement was observed for the compounds of the heavier halogens
resulting in the formation of B-H species via β-hydrogen elimination and intermediate
borenium cations.[2] Electron sextet chalcogen atoms were coordinated to yield
AlCPY heterocycles (Y = O, S, Se, Te). The P-Te moiety in 6 is stabilized by
coordination to the Lewis acidic aluminium atom, and a remarkable dimer is formed
in the solid state as a result of Te-Te interactions.
Figure 1.
References:
[1] C. Appelt, W. Uhl, et al. Angew. Chem. Int. Ed. 2011, 50, 3925.
[2] W. Uhl, C. Appelt, A. Wollschläger, A. Hepp, Inorg. Chem. 2014, 53, 8991.
Oral presentation - A06
Cooperative Lewis Acid/Base Catalysis
Devin Boom, Emmanuel Nicolas, Johan de Boed, Andreas W. Ehlers, J. Chris
Slootweg*
j.c.slootweg@vu.nl
Department of Chemistry and Pharmaceutical Sciences, VU University Amsterdam
De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
The discovery of single-bond activation at transition-metal centers has led to a
plethora of catalytic transformations, which highlights the power of organometallic
chemistry. Recently, main-group systems, such as group 15/13-based frustrated Lewis
pairs (FLPs), possessing a lone pair of electrons and a vacant orbital were also shown
to be able to catalytically activate chemical bonds.[1] As substrate, amine-boranes
have gained a lot of attention as potential hydrogen storage materials, and a variety of
transition metal complexes were reported as efficient dehydrogenation catalysts.[2]
However, the number of TM-free reagents is very limited and only a few systems
were reported to be catalytically active.[3] In this presentation, we describe the
dehydrogenation of amine-boranes using cooperative Lewis acid/base catalysis with
different pre-organized frustrated Lewis pairs.[4] In addition, a „rational catalyst
design“ approach to optimize this catalytic process will be presented and the impact
of this discovery for other acceptorless dehydrogenation reactions will be
illustrated.[5]
Figure 1. Rational catalyst design for the metal-free dehydrogenation of amine-boranes.
References:
[1] D.W. Stephan, Acc. Chem. Res. 2015, 48, 306.
[2] G. Alcaraz, S. Sabo-Etienne, Angew. Chem. Int. Ed. 2010, 49, 7170.
[3] C. Appelt, J.C. Slootweg, K. Lammertsma, W. Uhl, Angew. Chem. Int. Ed. 2013, 52, 4256.
[4] J.C. Slootweg, K. Lammertsma, et al. J. Am. Chem. Soc. 2012, 134, 201.
[5] C. Gunanathan, D. Milstein, Science 2013, 341, 249.
Oral presentation - A07
Boron-Cations and Radicals Stabilized by Strong P→B Interactions
M. Devillard, A. Rosenthal, G. Bouhadir, D. Bourissou
dbouriss@chimie.ups-tlse.fr
Laboratoire Hétérochimie Fondamentale et Appliquée
Paul Sabatier University, 118 route de Narbonne, 31062 Toulouse, France
Our group is interested in cooperative phenomena arising from ambiphilic
compounds. In this presentation, our recent studies on naphthyl-bridged phosphorusboron derivatives will be presented. The three following sub-topics will be discussed:
- Phosphine-boranes featuring strong, yet Lewis acid-responsive P→B interactions,[1]
- Phosphine-stabilized borenium salts featuring versatile reactivity,[2]
- Phosphine-stabilized boryl radicals: their electronic structure and chemical behavior.
Figure 1. Schematic representation of the naphthyl-bridged P/B derivatives
Acknowledgements: The CNRS, the Université Paul Sabatier and the Agence Nationale de la
Recherche are acknowledged for financial support of this work. We thank Dr. K. Miqueu (Université
de Pau et des Pays de l’Adour) for DFT calculations.
References:
[1] Bontemps, S.; Devillard, M.; Mallet-Ladeira, S.; Bouhadir, G.; Miqueu, K.; Bourissou, D. Inorg.
Chem. 2013, 52, 4714.
[2] Devillard, M.; Mallet-Ladeira, S.; Miqueu, K.; Bouhadir, G.; Bourissou, D. Angew. Chem. Int. Ed.
2015, DOI: 10.1002/anie.201500959.
Oral presentation - A08
Activation of π-Bonds Towards Cyclization Reactions using Lewis
Acidic Boranes
Rebecca L. Melen*
melenr@cardiff.ac.uk
School of Chemistry, Cardiff University
Main Building, Park Place, Cardiff, CF10 3AT, UK
Depletion of the π-electron density in alkenes and alkynes, by Lewis-acid
(electrophile) coordination, activates such groups to nucleophilic attack from amines,
phosphines, thiols, amides and/or other C-C π-bonds. In these reactions the Lewis
acid and Lewis base (nucleophile) undergo a 1,2-addition across the π-bond, reactivity
that has been observed in frustrated Lewis pair (FLP) chemistry.[1] Recently we have
established that main group ewis acids are capable of activating C≡C π-bonds
bearing intramolecular nucleophiles towards cyclization reactions yielding a diversity
of heterocycles containing B, N and O heteroatoms (Figure 1).[2-3] In some cases these
heterocycles can be formed catalytically in the absence of a transition metal. [2] Recent
developments will be discussed.
Figure 1. Cyclization reactions using boron Lewis acids.
References:
[1] R. L. Melen Chem. Commun., 2014, 50, 1161.
[2] R. L. Melen, M. M. Hansmann, A. J. Lough, A. S. K. Hashmi, D. W. Stephan Chem.-Eur. J. 2013,
19, 11928.
[3] M. M. Hansmann, R. L. Melen, F. Rominger, A. S. K. Hashmi, D. W. Stephan J. Am. Chem. Soc.
2014, 136, 777; M. M. Hansmann, R. L. Melen, F. Rominger, A. S. K. Hashmi, D. W. Stephan Chem.
Commun. 2014, 50, 7243.
Oral presentation - A09
Super-strained inorganic ligands: substrate-dependent reactivity
R. Streubel,* J. M. Villalba Franco, A. Espinosa Ferao, V. Nesterov
r.streubel@uni-bonn.de
Institut für Anorganische Chemie, Rheinischen-Friedrich-Wilhelms-Universität Bonn,
Gerhard-Domagk-Str. 1, GER-53121 Bonn
Recently, synthesis of complexes I ([M] = M(CO)5; E, E’ = NR) bearing superstrained inorganic P-ligands was achieved using Li/X phosphinidenoid metal
complexes and carbodiimides;[1] evidence for related transient species I (E = CR2,
E’ = O; E,E’ = O)[2,3] will be provided, too. First studies revealed a multifaceted,
substrate-dependent reactivity that is usable under mild conditions: exchange
reactions of the carbodiimide unit by other π-units (i),[4] facile ring opening with
acidic substrates such as H2O leading to zwitterionic complexes (ii),[1] ring-expansion
reactions using monoatomic building blocks such as chalcogen atoms (or others)
(iii),[5] or a substrate-responsive FLP-type reactivity (iv), i.e. ring-expansion using
isocyanates or carbon dioxide.[4] DFT calculated reaction pathways will be presented.
Figure 1. Reactivity of super-strained rings.
Acknowledgements: We are grateful to the DFG (STR 411/26-3) for financial support.
References:
[1] J. M. Villalba Franco, Takahiro Sasamori, G. Schnakenburg, A. Espinosa Ferao, R. Streubel, Chem.
Commun. 2015,51, 3878-3881.
[2] V. Nesterov, G. Schnakenburg, R. Streubel, to be published.
[3] C. Schulten, G. von Frantzius, A. Espinosa Ferao, G. Schnakenburg, R. Streubel, Chem. Sci. 2012,
3, 3526-3533.
[4] J. M. Villalba Franco, Takahiro Sasamori, G. Schnakenburg, A. Espinosa Ferao, R. Streubel, Chem.
Commun. 2015, submitted.
[5] J. M. Villalba Franco, G. Schnakenburg, R. Streubel, to be published.
Oral presentation - A10
Hetero deoxy-Breslow intermediates – and more
László Nyulászi,* Zsolt Kelemen
nyulaszi@mail.bme.hu
Department of Inorganic and Analytical Chemistry, Budapest University of
Technology and Economics
Műegyetem rkp 3, H-1111, Budapest, Hungary
N-heterocyclic carbenes (NHC) emerged as important stabilizing ligands in main
group chemistry.[1] With subvalent compounds X (CH2, SiH2, NH, PH, O, S) NHC
and the isomeric abnormal NHCs (aNHC) form stable deoxy-Breslow type mesoionic
compounds 1 and 2. These compounds have also possible H-shifted isomers 3 and 4,
which are themselves substituted aNHC and NHC, respectively. In a computational
analysis we present a comprehensive investigation on the relative stabilites of 1-4,
revealing that for the nitrogen and phosphorus compounds the energy of the two Hshifted forms (2 and 4) are close to each other, giving rise for a possible tautomeric
equilibrium, which can be fine-tuned by proper substituents. The relative stability of
the (substituted) abnormal carbenes (3) with respect to 4 does not depend on the type
of substituent. The stability of the mesoionic forms 1 and 2 is related to the
electronegativity of the heteroatom in X, the second and third row heteroatoms
exerting, however, different stabilization, which is related to the double bond energy.
NRT analysis revealed that the contribution of the double bonded resonance structures
for 1 and 2 is higher for the second than for the third row elements, which have larger
ionic contributions, in agreement with their large pz orbital contribution in the π-type
HOMO. NICS aromaticity is in accordance with the weight of the double bonded
resonance structures. The electronic structure and the double bond character of the
related compounds 1 and 2 with hypervalent heteroatoms X (SiR4, PR3, SR2) will also
be discussed.
Acknowledgements: OTKA K 105417 and COST CM1302 is gratefully acknowledged
References:
[1] (a) M. N. Hopkinson, C. Richter, M. Schedler, F. Glorius Nature 2014, 510, 485. (b) D. Martin, M.
Soleilhavoup, G. Bertrand Chem. Sci. 2011, 2, 389.
Oral presentation - A11
Unusual Reactivity of Alkali Metal Oligophosphanediides
Anup Kumar Adhikari, Ivana Jevtovikj, Peter Lönnecke, Evamarie Hey-Hawkins*
hey@uni-leipzig.de
Institute of Inorganic Chemistry, Universität Leipzig
Johannisallee 29, GER-04103 Leipzig
The chemistry of cyclic oligophosphorus compounds has developed impressively over
the last few decades. These species can exists as three-, four-, five-, and sixmembered rings and their stability and structures have been extensively
investigated.[1] In contrast, the targeted synthesis and properties of linear and cyclic
oligophosphanide anions have been studied in detail only recently. Some examples of
their reactivity have also been reported, and these studies already indicate a rich and
versatile chemistry.[2]
Recently, we have obtained a new type of neutral cyclic oligophosphane, namely N(tetramesityltetraphosphacyclopentylidene)cyclohexylamine, by the 1:2 reaction of
Na2P4Mes4 (Mes = 2,4,6-Me3C6H2) and cyclohexyl isocyanide. The corresponding
copper(I) complex was obtained by reaction with [CuBr(SMe2)]. In contrast, P−P
bond cleavage was observed in the reaction of Na2(P4Mes4) with nBuLi leading to a
phosphaindazole anion, (P2C9H9)‒ (Figure 1).[3]
Figure 1. Polymeric structure of sodium phosphaindazole anion; chains are oriented parallel
to the b axis. H atoms are omitted for clarity.
Acknowledgements: This work was supported by the DAAD (Deutscher Akademischer Austausch
Dienst, GSSP scholarship for A.K.A.), the Graduate School BuildMoNa and the EU COST Action
CM1302 Smart Inorganic Polymers (SIPs).
References:
[1] a) M. Baudler, Pure Appl. Chem., 1980, 52, 755; b) M. Baudler, K. Glinka, Chem. Rev., 1993, 93,
1623.
[2] a) S. Gómez-Ruiz, E. Hey-Hawkins, Coord. Chem. Rev., 2011, 255, 1360; b) I. Jevtovikj, P.
Lönnecke, E. Hey-Hawkins, Chem. Commun., 2013, 49, 7355.
[3] I. Jevtovikj, M. B. Sárosi, A. K. Adhikari, P. Lönnecke, E. Hey-Hawkins, Eur. J. Inorg. Chem.,
2015, in press.
Oral presentation - A12
Stable Silanetriols – Building Blocks for Rings and Cages
Rudolf Pietschnig
pietschnig@uni-kassel.de
Institute of Chemistry and CINSaT, University of Kassel
Heinrich-Plett-Strasse 40, 34132 Kassel, Germany
In neutral silanetriols the maximum number of polar silanol groups is attached to the
same silicon atom besides an organic substituent. Since the first preparation[1] and
structural characterization[2] the main research focus for this type of compounds has
been mainly devoted to their synthesis, solid state structures and conversion to
metallasiloxanes.[3,4] We are interested to extend the scope of this unusual class of
compounds to the liquid state and especially to solutions where aggregation and
micelle formation can be observed.[5,6] Besides their surfactant properties silanetriols
are also ideal precursors for controlled surface modifications.[7] Moreover, silanetriols
can be converted to rings and cages using controlled condensation reactions.[8,9]
References:
[1] T. Takiguchi, J. Am. Chem. Soc. 1959, 81, 2359.
[2] H. Ishida, J. L. Koenig, K. C. Gardner, J. Chem. Phys. 1982, 77, 5748.
[3] P. D. Lickiss, in Chemistry of Organic Silicon Compounds, Vol. 3 (Eds.: Z. Rappoport, Y.
Apeloig), Wiley, Chichester, UK, 2001, 695.
[4] Murugavel, R.; Voigt, A.; Walawalkar, M. G.; Roesky, H. W. Chem. Rev. 1996, 96, 2205.
[5] N. Hurkes, H. Ehmann, M. List, S. Spirk, M. Bussiek, F. Belaj, R. Pietschnig, Chem. Eur. J. 2014,
20, 9330.
[6] S. Spirk, S. Salentinig, K. Zangger, F. Belaj, R. Pietschnig, Supramol. Chem. 2011, 23, 801.
[7] S. Spirk, H. Ehmann, M. Reischl, R. Kargl, N. Hurkes, M. Wu, J. Novak, R. Resel, R. Pietschnig,
V. Ribitsch, Appl. Mat. Interf. 2010, 2, 2956.
[8] S. Spirk, M. Nieger, F. Belaj, R. Pietschnig, Dalton Trans. 2009, 163.
[9] N. Hurkes, C. Bruhn, F. Belaj, R. Pietschnig, Organometallics 2014, 33, 7299.
Oral presentation - A13
Cyclic Derivatives of Group 14 in Material Science
H. Amenitsch, J. Binder, A. Torvisco, M. Wolf, C. Zeppek, F. Uhlig*
frank.uhlig@tugraz.at
Institute of Inorganic Chemistry, Graz University of Technology
Stremayrgasse 9, A-8010 Graz, Austria
Cyclic silicon, germanium and/or tin containing derivatives are a well explored field
in organometallic chemistry. Over the years our institute has also reported on the
syntheses of novel compounds of this type. In extension of this work, we will present
here on the synthesis and characterization of such derivatives as well as their
applications in material science. We discuss here the synthesis and analytical
characterization of a series of novel compounds of type (R2E)n (n = 4-7; R = aryl, H;
E = Si, Ge, Sn) displaying in some cases a surprising reaction behavior. Furthermore
reactions for the formation of nanoparticles by using such derivatives as precursors
are presented together with preliminary results of their use in novel energy storage
materials. All compounds are characterized by state-of-the-art analytical methods
including scattering techniques and electrochemical characterizations.
Figure 1. Core-shell tin nanoparticles
Acknowledgements: The NAWI Graz-project is gratefully acknowledged for the financial support of
this work. Furthermore, we thank ELETTRA Synchrotrone Trieste for their outstanding collaboration.
Oral presentation - A14
Captivating Organotin Anions – Cages, Rings and Chains
Roland C. Fischer,* Michaela Flock, Michael S. Hill, David J. Liptrot, Kathrin
Schittelkopf, Beate Steller
Roland.Fischer@tugraz.at
Institute for Inorganic Chemistry, Graz University of Technology,
Stremayrgasse 9/V, A-8010 Graz, Austria
Owing to the high reactivity of the tin-hydrogen bond, aryltinhydrides are versatile
building blocks for the formation of oligo- and polystannanes. Therefore, we
investigated the reactivity of diphenyltindihydride against alkali metals and alkali
metal reagents. In the course of our studies, we developed convenient and high-yield
routes towards a surprisingly rich variety of bicyclic, cyclic and acyclic mono-, diand tri-metallated oligostannanes. (Fig. 1).
Mechanistic investigations of the Sn-Sn bond formation allowed for the directed
synthesis of the title compounds. Trends in their chemical reactivity together with
structural and spectroscopic properties will be discussed.
Figure 1. Bicyclic, cyclic and acyclic oligostannides derived from Ph2SnH2.
Acknowledgements: The COST action CM1302 ‘Smart Inorganic Polymers’ is gratefully
acknowledged.
References:
[1] a) P. Riviere, A: Castel, M. Riviere-Baudet, Alkaline and alkaline earth metal-14 compounds in:
The Chemistry of organic germanium, tin and lead compounds, Vol. 2 Part 1. (Ed Z. Rappoport),
Wiley, Chichester, 2002, p 653ff. b) C. Zeppek, A. Torvisco, R. C. Fischer, F. Uhlig, Can. J. Chem.,
2014, 92, 556. c) K. Schittelkopf, R. C. Fischer, S. Meyer, P. Wilfling, F. Uhlig, Appl. Organomet.
Chem., 2010, 24, 897. d) T. Schollmeier, U. Englich, R. Fischer, I. Prass, K. Ruhlandt, M. Schürmann,
F. Uhlig, Z. Naturforsch. B, 2004, 59b, 1462.
Oral presentation - A15
Transformations of Small Inorganic Molecules by Low-valent
Transition Metalate Anions and Transition Metal Radicals
Robert Wolf,* Uttam Chakraborty,(a) Stefan Pelties,(a) Niels van Velzen,(b) and
Sjoerd Harder(b)
robert.wolf@ur.de
(a) University of Regensburg, Institute of Inorganic Chemistry, D-93040 Regensburg;
(b) Chair of Inorganic and Organometallic Chemistry, University ErlangenNürnberg, Egerlandstraße 1, D-91058 Erlangen
This talk will discuss the chemistry of new low-oxidation state cyclopentadienyl iron,
cobalt and nickel complexes. The first part will describe the synthesis of Nheterocyclic carbene-stabilized cyclopentadienylnickel(I) radicals.[1] The complexes
have a modular structure that allows the modification of their steric and electronic
properties. The reactivity of these new nickel(I) radicals with radical traps such as
white phosphorus and elemental sulfur will be examined. The second part will discuss
the chemistry of new pentarylcyclopentadienyl complexes.[2] These uncommon Cp
derivatives are able to stabilize compounds with unusual structures and reactivity
patterns as illustrated for example by the synthesis of the first
tetraphosphacyclobutadiene iron complex, [CpAr5Fe(cyclo-P4)]- and the dinuclear
hexasulfide [(CpAr5Ni)2(µ-S6)] (Figure 1).
Figure 1. Reactivity of new cyclopentadienyl iron and nickel complexes.
Acknowledgements: We thank Moritz Modl and Prof. Manfred Scheer (University of Regensburg) for
collaborating on CpBig chemistry.
References:
[1] S. Pelties, D. Herrmann, B. de Bruin, F. Hartl, R. Wolf, Chem. Commun. 2014, 50, 7014-7016.
[2] a) W. Kläui, L. Ramacher, Angew. Chem. Int. Ed. Engl. 1986, 25, 97-98; b) H. Schumann, A.
Lentz, R. Weimann, J. Pickardt, Angew. Chem. Int. Ed. Engl. 1994, 33, 1731-1733; c) C. Ruspic, J. R.
Moss, M. Schürmann, S. Harder, Angew. Chem. Int. Ed. 2008, 47, 2121-2126.; d) L. D. Field, C. M.
Lindall, A. F. Masters, G. K. B. Clentsmith, Coord. Chem. Rev. 2011, 255,1733-1790.
Oral presentation - A16
Pyramidanes: the Covalent Form of an Ionic Compound
V. Lee,1* O. Gapurenko,2 Y. Ito,1T. Meguro,1H. Sugasawa,1A. Sekiguchi,1 R.
Minyaev,2V. Minkin,2H. Gornitzka,3R. Herber4
leevya@chem.tsukuba.ac.jp
1
Department of Chemistry, University of Tsukuba
University of Tsukuba, Japan; 2Southern Federal University, Rostov on Don, Russia;
3
Université de Toulouse, France; 4Hebrew University, Israel
Pyramidanes, the square-pyramidal compounds, represent a novel highly challenging
class of strained polyhedral clusters featuring an “invertedly” tetrahedral apical atom.
Well-studied on theoretical grounds, pyramidane and its derivatives eluded
experimental realization until very recently. In this presentation, we report on a series
of the first ever prepared group 14 element pyramidanes 1 with the C4/Si4/Ge4 -bases
and Ge/Sn/Pb-apexes (Figure).[1] Based on the combined experimental [X-ray
crystallography, 13C and 119Sn NMR spectroscopy, Mössbauer spectroscopy,
reactivity studies] and computational [frontier MO, NBO/NPA, topological analysis
(AIM and ELF)] data, we found a remarkable lone pair character at the apical atom
E’. This gives rise to a high degree of ionicity in the E’–E apex-to-base bonds and
thus notable contribution of the {[E4]2––[E’]2+} cyclobutadiene dianion–apical atom
dication ionic resonance form to the overall composition of the formally neutral
pyramidanes.
Figure 1. Pyramidanes 1.
Acknowledgements: This work was supported by the Japanese Society for the Promotion of Science
(23655027, 24245007, 24550038, 90143164), Russian Foundation for Basic Research (14-03-92101)
and Russian Scientific Schools (NSh-274.2014.3).
References:
[1] (a) V. Ya. Lee, Y. Ito, A. Sekiguchi, H. Gornitzka, O. A. Gapurenko, V. I. Minkin, R. M. Minyaev,
J. Am. Chem. Soc., 2013, 135, 8794; (b) V. Ya. Lee, Y. Ito, O. A. Gapurenko, A. Sekiguchi, V. I.
Minkin, R. M. Minyaev, H. Gornitzka, Angew. Chem. Int. Ed., 2015, 54, Early View [DOI:
10.1002/anie.201500731].
Oral presentation - A17
Stable N-Heterocyclic Carbenes with a 1,1’-Ferrocenediyl Backbone
and Their Heavier Homologues
Ulrich Siemeling*, Christian Färber, Jan Oetzel, Michael Leibold, Clemens Bruhn
siemeling@uni-kassel.de
Institute of Chemistry, University of Kassel
Heinrich-Plett-Str. 40, GER-34132, Kassel
N-Heterocyclic carbenes (NHCs)[1] are extremely valuable as nucleophilic
organocatalysts. They are widely applied as ligands in transition-metal catalyzed
reactions, where they are known as particularly potent σ-donors. They are commonly
viewed as workhorses exhibiting reliable, but undramatic, chemical behavior. We
recently demonstrated that a stable ferrocene-based NHC (Fig. 1, left) is able to add
ammonia, methyl acrylate, tert-butyl isocyanide, and carbon monoxide under mild
conditions.[2] Such small-molecule activation reactions are typical of
(alkyl)(amino)carbenes, but were completely unprecedented for diaminocarbenes.[3]
In view of the surprising reactivity of this ferrocene-based NHC, which is due to its
ambiphilic nature,[4] we surmised that its heavier homologues (Fig. 1, right), too, can
be expected to show exceptional chemical behavior. While the synthesis and isolation
of corresponding germylenes and stannylenes turned out to be easily possible, we are
still hot on the heels of stable or persistent silylenes and plumbylenes. We have been
able to obtain a persistent silylenoid, and we have structurally characterized the C-H
activation product of a reactive plumbylene.
Figure 1. A stable ferrocene-based NHC (XRD result, left) and its heavier homologues
(right).
Acknowledgements: We are grateful to the DFG for generous funding.
References:
[1] M. N. Hopkinson, C. Richter, M. Schedler, F. Glorius, Nature 2014, 510, 485.
[2] U. Siemeling, C. Färber, C. Bruhn, M. Leibold, D. Selent, W. Baumann, M. von Hopffgarten, C.
Goedecke, G. Frenking, Chem. Sci. 2010, 1, 697.
[3] D. Martin, M. Soleilhavoup, G. Bertrand, Chem. Sci. 2011, 2, 389.
[4] C. Goedecke, M. Leibold, U. Siemeling, G. Frenking, J. Am. Chem. Soc. 2011, 133, 3557.
Oral presentation - A18
Sila- and Germacyclopentadienyl Based Radicals
C. R. W. Reinhold, B. Urschel, T. Müller*
thomas.mueller@uni-oldenburg.de
Institute of Chemistry
Carl von Ossietzky University Oldenburg Carl von Ossietzky Straße 9-11, D-26129
Oldenburg, FRG
The remarkable electronic and photophysical properties of group 14 elementcyclopentadienes (tetroles) are well-described and already found applications in
OLEDs.[1,2] The results of quantum mechanical calculations predict a stability for the
corresponding tetrolyl radicals similar to that of the well-investigated aroxyl based
radicals and polyradicals. The addition of unpaired spins to the tetroles could lead to
new materials with interesting properties.[3] In this contribution, we will report on our
attempts to generate silolyl and germolyl radicals either by reaction of persistent
radicals with H-tetroles (Figure, eq. 1) or by reduction of the corresponding halides
(Figure, eq. 2)
Figure 1. Synthesis of tetrolyl radicals and ESR spectra of the corresponding germanium(left) and silicon- (right) centered radicals.
Acknowledgements: This work is supported by the CvO University. We thank Drs. Boris Tumanskii
and Dmitri Bravo-Zhivotovskii for many valuable discussions.
References:
[1] J. Dubac, A. Laporterie, G. Manuel, Chem. Rev. 1990,90, 215.
[2] S. Yamaguchi, K. Tamao, J. Chem. Soc., Dalton Trans. 1998,3693.
[3] T. Nozawa, A. Sekiguchi, M. Ichinohe J. Am. Chem. Soc. 2011, 133, 5773.
Oral presentation - A19
Reactions of tricyclopentasilane and related cyclic silicon compounds
with bulky alkyl substituents
Takeaki Iwamoto,* Naohiko Akasaka, Shintaro Ishida
iwamoto@m.tohoku.ac.jp
Department of Chemistry, Graduate School of Science, Tohoku University
6-3 Aramakiazaaoba, Aoba-ku, Sendai 980-8578, Japan
Polycyclic oligosilanes (molecular silicon clusters) have been extensively studied
because they exhibit unique electronic structures due to delocalization of σ(Si–Si)
electrons over the silicon frameworks. Recently several molecular silicon clusters
bearing three-coordinate silicon vertices with no substituents and/or highly strained
four-coordinate silicon vertices in the silicon frameworks (siliconoids[1f]) have been
synthesized and their unique structures and reactions are investigated.[1] One of the
fascinating reactions is a disproportionation reaction involving expansion or
contraction of the silicon frameworks. Scheschkewitz and coworkers have
demonstrated thermal disproportionation reactions of an Si6R6 isomer.[1f] Very
recently we have synthesized peralkyltricyclo[2.1.0.01,3]pentasilane 1 (Chart 1) and
found that it undergoes thermal disproportionation reactions to give new molecular
silicon cluster 2.[2] Detailed analysis of the thermal reaction of 1 indicated that
tetrasilabicyclo[1.1.0]but-1(2)-ene 3 resulting from elimination of dialkylsilylene unit
4 from 1 was a key intermediate for formation of 2. In the present paper, we wish to
report on recent results on thermal reaction of 1 and related molecular silicon clusters.
Figure 1. Compounds 1-4
References:
[1] (a) D. Scheschkewitz, Angew. Chem. Int. Ed. 2005, 44, 2954. (b) G. Fischer, V. Huch, P. Mayer, S,
K. Vasisht, M. Veith, N. Wiberg, Angew. Chem. Int. Ed. 2005, 44, 7884. (c) D. Nied, R. öppe, W.
Klopper, H. Schnöckel, F. Breher, J. Am. Chem. Soc. 2010, 132, 10264. (d) K. Abersfelder, A. J. P.
White, H. S. Rzepa, D. Scheschkewitz, Science 2010, 327, 564. (e) K. Abersfelder, A. J. P, White, R. J.
F.; Berger, H. S. Rzepa, D. Scheschkewitz, Angew. Chem., Int. Ed. 2011, 50, 7936 (f) K. Abersfelder,
A. Russell, H. S. Rzepa, A. J. P. White, P. R. Haycock, D. Scheschkewitz, J. Am. Chem. Soc. 2012,
134, 16008.
[2] T. Iwamoto, N. Akasaka, S. Ishida, Nat. Commun. 2014, 5, 5353.
Oral presentation - A20
Synthesis of 1,2-Digermacyclobutene Derivatives and Their
Reactions with Ethylene
Takahiro Sasamori,* Tomohiro Sugahara, Tomohiro Agou, Koh Sugamata, JingDong Guo, Shigeru Nagase, and Norihiro Tokitoh
sasamori@boc.kuicr.kyoto-u.ac.jp
Institute for Chemical Research, Kyoto Univ.
Gokasho, Uji, Kyoto 611-0011, JAPAN
Triple-bond compounds between heavier group 14 elements, group 14 dimetallynes,
have attracted many chemists from the viewpoints of their unique physical and
chemical properties.[1] Although these multiple bond compounds are difficult to be
isolated due to their inherent extremely high reactivity towards the addition reaction
with moisture and/or aerobic oxygen and self-oligomerization, it has been evidenced
that such reactive species can be isolated when they are well kinetically stabilized by
sterically demanding substituents with keeping their intrinsic nature of reactivity.
Nowadays, many examples of the stable group 14 dimetallynes have been reported.
Reactions of the stable disilynes with alkenes were reported to give the corresponding
1,2-disilacyclobutene derivatives via formal [2+2] cycloaddition reactions.[2] Here we
will report the synthesis and isolation of the stable 1,2-digermacyclobutene by
reactions of the stable digermyne, BbtGeGeBbt (Bbt = 2,6-[CH(SiMe3)2]-4[C(SiMe3)3]-C6H2),[3] with alkenes. In addition, the chemical and physical properties
of the obtained 1,2-digermacyclobutenes will also be described.
References:
[1] R. C. Fischer, P. P. Power, Chem. Rev. 2010, 110, 3877.
[2] (a) R. Kinjo, M. Ichinohe, A. Sekiguchi, N. Takagi, M. Sumimoto, S. Nagase, J. Am. Chem. Soc.
2007, 129, 7766. (b) N. Wiberg, S. K. Vasisht, G. Fischer, P. Mayer, Z. Anorg. Allg. Chem. 2004, 630,
1823.
[3] Y. Sugiyama, T. Sasamori, Y. Hosoi, Y. Furukawa, N. Takagi, S. Nagase, N. Tokitoh, J. Am.
Chem. Soc. 2006, 128, 1023.
Oral presentation - A21
Synthesis, Molecular Structure and Reactivity of Cyclic Sn–P-Lewis
Pairs
S. Freitag, K. Krebs, J. Schneider, L. Wesemann*
lars.wesemann@uni-tuebingen.de
Institut für Anorganische Chemie, University of Tübingen
Auf der Morgenstelle 18, 72076 Tübingen
Chemistry of intramolecular stannylene based Lewis pairs is presented.[1] Starting
with the terphenyl substituted tin chloride ArSnCl the cyclic molecules 1 and 2 were
synthesized in high yield following a straightforward nucleophilic substitution at the
tin atom (Equation 1).[2] The substitution products 1 and 2 show an intramolecular
Sn–P bond in solution and solid state. The reactivity of these cyclic molecules
towards olefins (3), alkynes (4), aldehydes, ketones and azides is discussed (Equation
2). In the case of 1-pentene we found reversible and regioselective addition of the
olefin to give the cyclopentane 3. Furthermore in reaction with transition metal
fragments of the nickel triad the Lewis pairs 1 and 2 show coordination of tin and
phosphorus at the transition metal. In dependency on the coordinating co ligand or
temperature the stannylene moiety exhibits a switch from donor (5) to acceptor (6)
character (Equation 3).[3]
Figure 1. Equation 1-3 (Ar =C6H3-2,6-Trip2, Trip = C6H2-2,4,6-iPr3, R` = SiMe3, Ph, R = iPr)
References:
[1] a) S. Freitag, J. Henning, H. Schubert, L. Wesemann, Angew. Chem., Int. Ed. 2013, 52, 5640-5643;
b) S. Freitag, K. M. Krebs, J. Henning, J. Hirdler, H. Schubert, L. Wesemann, Organometallics 2013,
32, 6785-6791.
[2] B. E. Eichler, L. Pu, M. Stender, P. P. Power, Polyhedron 2001, 20, 551-556.
[3] K. M. Krebs, S. Freitag, H. Schubert, B. Gerke, R. Pöttgen, L. Wesemann, Chem.-Eur. J. 2015, in
press.
Oral presentation - A22
Synthesis, Structures and Reactions of Antiaromatic Organolead
Compounds Stabilized by Lewis Bases
Masaichi Saito* (a) Tomoki Akiba,(a) Marisa Nakada,(a) Misumi Kaneko, (a)
Shunsuke Furukawa,(a) Mao Minoura,(b) Masahiko Hada(c)
masaichi@chem.saitama-u.ac.jp
(a) Department of Chemistry, Graduate School of Science and Engineering, Saitama
University, Shimo-okubo, Sakura-ku, Saitama-city, Saitama, 338-8570, JAPAN
(b) Department of Chemistry, Graduate School of Science and Engineering, Tokyo
Metropolitan University
(c) Department of Chemistry, College of Science, Rikkyo University
Antiaromaticity, first proposed by Breslow,[1] is used to explain peculiar instability of
the cyclic conjugated compounds with 4np electrons. However, antiaromaticity of
compounds with heavy group 1 atoms in the π-frameworks remains elusive, even
though a few analogues of cyclobutadiene containing heavy group 14 atoms have
already been synthesized.[2] We focus on metallacyclopentadienylidene as another
possible antiaromatic compound bearing a heavy group 14 atom in the skeleton. In the
course of our studies on organolead compounds with unique electronic structures,[3]
we report herein the synthesis of a base-stabilized plumbacyclopentadinylidene 1
from 1,4-dilithio-1,3-butadiene 2[4] and its reactivity and behavior in solution.[5]
Figure 1. Synthesis of Base-stabilized Plumbacyclopentadienylidene
References:
[1] R. Breslow, Acc. Chem. Res. 1973, 6, 393.
[2] (a) C. Cui, M. M. Olmstead, P. P. Power, J. Am. Chem. Soc. 2004, 126, 5062; (b) K. Suzuki, T.
Matsuo, D. Hashizume, H. Fueno, K. Tanaka, K. Tamao, Science 2011, 331, 1306; (c) S. Inoue, W. Y.
Wang, C. Prasang, M. Asay, E. Irran, M. Driess, J. Am. Chem. Soc. 2011, 133, 2868; (d) Y. –F. Yang,
G. –J. Cheng, J. Zhu, X. Zhang, S. Inoue, Y. –D. Wu, Chem. Eur. J. 2012, 18, 7516; (e) H-X. Yeong,
H-W. Xi, Y. Li, S. B. Kunnappilly, B. Chen, K-C. Lau, H. Hirao, K. H. Lim, C-W. So, Chem. Eur. J.
2013, 19, 14726.
[3] M. Saito, M. Sakaguchi, T. Tajima, K. Ishimura, S. Nagase, M. Hada, Science 2010, 328, 339.
[4] M. Saito, M. Nakamura, T. Tajima, M. Yoshioka, Angew. Chem., Int. Ed. 2007, 46, 1504.
[5] (a) M. Saito, T. Akiba, M. Kaneko, T. Kawamura, M. Abe, M. Hada, M. Minoura, Chem. Eur. J.
2013, 19, 16946; (b) T. Kawamura, M. Abe, M. Saito, M. Hada, J. Comput. Chem. 2014, 35, 847; (c)
M. Saito, M. Nakada, T. Kuwabara and M. Minoura, Chem. Commun. 2015, 51, 4674.
Oral presentation - A23
Chemistry Applying Metalloid Tin Clusters
Andreas Schnepf, Claudio Schrenk
andreas.schnepf@uni-tuebingen.de
Department of Chemistry, University of Tübingen
Auf der Morgenstelle 18, 72076 Tübingen
Starting from Sn(I) halides, available via a preparative co condensation technique we
could establish a fruitful route to metalloid tin clusters in recent years.[1] These
clusters give us a first direct insight into the fascinating area between molecules and
the solid state,[2] whereby we could show that novel structural motives are realized in
this borderland. Hence zentaurpolyhedral arrangements of 10 tin atoms in such
metalloid clusters seem quite favorable, e.g. within the neutral metalloid cluster
Sn10[Si(SiMe3)3]6 1.[3] However, the cluster core of 1 is completely shielded by the
ligand shell and thus subsequent reactions are difficult as the reactive naked tin atoms
are not available. Applying now a Sn(I)Cl solution for the synthesis of metalloid
clusters we were able to obtain the open anionic metalloid tin cluster
[Sn10[Si(SiMe3)3]4]2- 2[4] in quite high yield. In 2 the tin atoms are now incompletely
shielded by the ligand shell so that subsequent reactions seem possible. Hence a first
step towards chemistry with metalloid clusters was done and we describe first
investigations concerning the physical and chemical properties of 2.
Figure 1. Molecular Structure of [Sn10[Si(SiMe3)3]4]2- 2
References:
[1] C. Schrenk, R. Köppe, I. Schellenberg, R. Pöttgen, A. Schnepf, Z. Anorg. Allg. Chem. 2009, 635,
1541-1548.
[2] A. Schnepf, Angew. Chem. Int. Ed. 2004 43, 664 – 666, A. Schnepf, Chem. Soc. Rev. 2007, 36,
745-758.
[3] C. Schrenk, I. Schellenberg, R. Pöttgen, A. Schnepf, Dalton Trans. 2010, 39, 1872 – 1876.
[4] C. Schrenk, A. Kubas, K. Fink, A. Schnepf, Angew. Chem. Int. Ed. 2011 50, 7237 – 7277. C.
Schrenk, F. Winter, R. Pöttgen, A. Schnepf, Chemistry, 2015, DOI: 10.1002/chem.201405595.
Oral presentation - A24
Ternary Intermetalloid Clusters: About Unexpected Structures and
How to Get There
Stefanie Dehnen*
dehnen@chemie.uni-marburg.de
Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften,
Philipps-Universität Marburg
Hans-Meerwein-Straße, D-35032 Marburg, Germany
Heterometallic cluster compounds are currently actively investigated by many
research groups, leading from structural studies through functional analyses to the
generation of innovative materials.[1] Binary main group element aggregates
[E13/14xE14/15y]q– (E13/14/15 = Ga, In, Tl; Ge, Sn, Pb; As, Sb, Bi), hence binary Zintlanions, proved to be useful synthetic tools in reactions with transition metal
compounds for assembling ternary intermetalloid clusters [MxE13/14yE14/15z]q–.[2] The
latter possess a large variety of different structural motifs and corresponding
electronic properties, subject to the nature of the involved elements. Unprecedented,
non-classical structures helped to gain deeper insight in the formation of such
aggregates (see Figure).[7]
Figure 1. Formation of non-deltahedral intermetalloid clusters from a deltahedral precursor
Acknowledgements: This work was supported by Deutsche Forschungsgemeinschaft, Alexander von
Humboldt Stiftung and Friedrich Ebert Stiftung
References:
[1] S. Scharfe, F. Kraus, S. Stegmaier, A. Schier, T. F. Fässler, Angew. Chem. Int. Ed. 2011, 50, 3630.
[2] F. Lips, R. Clérac, S. Dehnen, J. Am. Chem. Soc. 2011, 133, 14168.
[3] F. ips, M. Hołyńska, R. Clerac, U. inne, I. Schellenberg, R. Pöttgen, F.Weigend, S. Dehnen, J.
Am. Chem. Soc. 2012, 134, 1181.
[4] R. Ababei, W. Massa, K. Harms, X. Xie, F. Weigend, S. Dehnen, Angew. Chem. Int. Ed. 2013, 52,
13544.
[5] B. Weinert, F. Müller, K. Harms, S. Dehnen, Angew. Chem. Int. Ed. 2014, 53, 11979.
[6] B. Weinert, A.R. Eulenstein, R. Ababei, S. Dehnen, Angew. Chem. Int. Ed. 2014, 53, 4704.
[7] S. Mitzinger, L. Broeckaert, W. Massa, F. Weigend, S. Dehnen, 2015, submitted.
Oral presentation - A25
Base-Stabilized Low Valent Group 14 Element Complexes for the
Construction of Unsaturated Systems
Cheuk-Wai So
CWSo@ntu.edu.sg
Division of Chemistry and Biological Chemistry, School of Physical and
Mathematical Sciences, Nanyang Technological University
21 Nanyang Link, 637371 Singapore
The base-stabilized group 14 element(I) dimers can serve as synthons for the
preparation of group 14 elements-containing aromatic/delocalized π-conjugated
systems. Firstly, the first examples of the 2,6-diiminophenyl-stabilized germanium(I),
tin(I) and lead(I) dimers [{2,6-(CH=NAr)2C6H3}E:]2 (E = Ge, Sn, Pb; Ar = 2,6iPr2C6H3) can be reduced by alkali metal to form novel aromatic low valent group 14
analogue of indenyl anions [{2,6-(CH=NAr)2C6H3}E:]- and the radical anion [{2,6(CH=NAr)2C6H3}Ge:]·- (1).[1] Secondly, the reaction of the amidinate-stabilized
silicon(I) dimer [PhC(NtBu)2Si:]2 with two equivalents of the amido trichlorosilane
[L’SiCl3] (L’ = 2,6-iPr2C6H3NSiMe3) and six equivalents of KC8 afforded the
extensive n, π, σ-electron delocalized Si4ring [LSi(µ-SiL’)2SiL] (2).[2] In addition, a
germanium atom in the zero oxidation state stabilized by the N-heterocylic silylene 3
will be described.[3]
Figure 1. Group 14 elements-containing unsaturated systems
Acknowledgements: This work was supported by ASTAR SERC PSF Grant
References:
[1] a) S.-P. Chia, R. Ganguly, Y. Li, C.-W. So, Organometallics 2012, 31, 6415; b) S.-P. Chia, H.-X.
Yeong, C.-W. So, Inorg. Chem. 2012, 51, 1002; c) S.-P. Chia, H.-W. Xi, Y. Li, K. H. Lim, C.-W. So,
Angew. Chem. Int. Ed. 2013, 52, 6298; d) S.-P. Chia, E. Carter, H.-W. Xi, Y. Li, C.-W. So, Angew.
Chem. Int. Ed. 2014, 53, 8455.
[2] S.-H. Zhang, H.-W. Xi, K. H. Lim, C.-W. So, Angew. Chem. Int. Ed. 2013, 52, 12346.
[3] Y.-L. Shan, W.-L. Yim, C.-W. So, Angew. Chem., Int. Ed. 2014, 53, 13155.
Oral presentation - A26
Anion and Cation Complexation by Di- and Multicentered Tin-Based
Lewis Acids
Klaus Jurkschat*
klaus.jurkschat@tu-dortmund.de
Fakultät für Chemie und Chemische Biologie, TU Dortmund
Dortmund, GER-44227
In a revival of our earlier interest in di-and multicentered Lewis acids (types A – D) as
hosts for anions [1] first results on compounds of types E and F, and related
derivatives are reported. Most remarkably, reaction of the compound HC(SnPh2F)3
with fluoride anion reproducibly gives, under partial Sn-C bond cleavage, the
unprecedented nona-nuclear tin cluster G.
References:
[1]
A. S. Wendji, M. Lutter, C. Dietz, V. Jouikov, K. Jurkschat Organometallics 2013, 32, 5720 (and
references cited herein).
Oral presentation - A27
New isolated polyborate anions templated by cationic transitionmetal complexes
Michael A. Beckett*,(a) Mohammed A. Altahan,(a) and Peter N. Horton(b)
m.a.beckett@bangor.ac.uk
(a) School of Chemistry, Bangor University, Bangor, Gwynedd, LL57 2UW, UK
(b) School of Chemistry, Southampton University, Southampton, SO17 1BG, UK
Polyborate anions are conveniently classified as either ‘condensed’ (2D or 3D
polymeric chains, sheets or networks) or ‘isolated’ (discrete anionic moieties).
Isolated polyborate anions are readily synthesised by the addition of B(OH)3 to a basic
aqueous solution containing templating cations, or by solvothermic methods.
Templated products arise since B(OH)3in basic aqueous solution exists as a dynamic
combinatorial library of polyborate anions. In general, pentaborate(1-) salts
(containing the [B5O6(OH)4]- anion) are formed because these salts have a strong Hbonded anionic lattice, which is sufficiently flexible to accommodate many medium
sized cations.[1] Salts containing polyborate anions other than pentaborate(1-) are
relatively rare. We are interested in the synthesis of structurally novel polyborate
anions and have adopted a strategy of templating such species by the use of sterically
demanding and/or highly charged cations. Herein, we report the synthesis of several
salts containing isolated polyborate anions partnered with transition metal cations and
describe the synthesis and structures of novel heptaborate(3-) and octaborate(2-)[2]
anions. These anions contain numerous fused B-O rings and cages.
References:
[1] (a) M.A. Beckett, S.J. Coles, R.A. Davies, P.N. Horton and C.L. Jones, Dalton Trans., 2015, 44, in
press. (Published online 10.3.15) DOI: 10.1039/c5dt00248f. (b) M.A. Beckett, P.N. Horton, M.B.
Hursthouse, D.A. Knox, and J.L. Timmis, Dalton Trans, 2010, 39, 3944-3951.
[2] M.A. Altahan, M.A. Beckett, S.J. Coles and P.N. Horton, Inorg. Chem., 2015, 54, 412-414.
Oral presentation - B01
Reactivities of a Barrelene-type Dialumane as an Equivalent of an
Al=Al Doubly-bonded Species
Tomohiro Agou, Koichi Nagata, Takahiro Sasamori, and Norihiro Tokitoh*
agou@boc.kuicr.kyoto-u.ac.jp
Institute for Chemical Research, Kyoto University
Gokasho, Uji, Kyoto 611-0011, Japan
Construction of novel element-element bonding has been one of the most important
topics in chemistry. However, multiply-bonded compounds involving heavier group
13 elements have remained underdeveloped.[1] Especially, a dialumene (R–Al=Al–R)
has never been isolated as a stable compound under ambient conditions. Generation of
a 1,2-diaryldialumene was suggested from the isolation of the corresponding [2+4]cycloadduct of the dialu-mene with toluene.[2] In the course of our synthetic studies on
dialumenes, we have found that a dialumane (Al–Al singly-bonded species) bearing
barrelene-like scaffold ex-hibits reactivities as a synthetic equivalent of the
corresponding dialumene.[3-5] The C6H6 moiety of barrelene-type dialumane 1 is
readily exchanged with naphtha-lene and bis(trimethylsilyl)acetylene at room
temperature, affording the corresponding cyclic dialumanes 2 and 3 (Scheme 1).
Formation of dialumanes 2 and 3 are most likely interpreted in terms of the
intermediacy of dialumene 4 via thermal retro-cycloaddition of barrelene-type
dialumane 1. Reactions of dialumane 1 with other unsaturated compounds as well as
transition metal complexes will also be described.
Scheme 1
References:
[1] R. C. Fischer, P. P. Power, Chem. Rev. 2010, 110, 3877.
[2] R. J. Wright, A. D. Phillips, P. P. Power, J. Am. Chem. Soc. 2003, 125, 10784.
[3] T. Agou, K. Nagata, N. Tokitoh, Angew. Chem. Int. Ed. 2013, 52, 10818.
[4] K. Nagata, T. Agou, N. Tokitoh, Angew. Chem. Int. Ed. 2014, 53, 3881.
[5] T. Agou, K. Nagata, T. Sasamori, N. Tokitoh, Chem. Asian J. 2014, 9, 3099.
Oral presentation - B02
Donor-acceptor complexes of inorganic analogs of benzene
Alexey Y. Timoshkin
a.y.timoshkin@spbu.ru
Department of Inorganic Chemistry, Institute of Chemistry, St. Petersburg State
University
Universitetskii pr. 26, 198504 St. Petersburg, Russia
Results of experimental and theoretical studies of inorganic benzene analogs:
borazine, substituted borazines, polyborazines, alumazene and their donor-acceptor
complexes will be presented. Structural and energetic aspects of complex formation
and thermal stability of heterocycles and their complexes will be discussed. It is
experimentally shown, that solution of B,B’,B”-tribromborazine in deuterobenzene is
stable for 14 months, but undergoes fast (within minutes) H/D exchange in presence
of Lewis acid AlBr3. Proposed electrophilic substitution mechanism for the exchange
is supported by computational studies. In contrast, unsubstituted borazine does not
undergo H/D exchange in presence of AlBr3. Hydrogenation reactions of heterocycles
will be also discussed. Quantum chemical computations at B3LYP/TZVP level of
theory indicate that upon complexation with AlCl3 as a model Lewis acid, both
endothermicity and activation energies of hydrogenation processes of borazine
(Figure) and polyborazines are significantly reduced. The use of Lewis acids as
catalysts in the processes of regeneration of spent hydrogen fuel is recommended.
Figure 1. Energy profile of the hydrogenation process of borazine (red) and its complex with
AlCl3 (blue). B3LYP/TZVP level of theory.
Acknowledgements: Financial support from St. Petersburg State University (grant 12.38.255.2014) is
acknowledged.
References:
Lisovenko A.S., Timoshkin A.Y., Inorg. Chem. 2010, 49, 10357–10369. Timoshkin A.Y., Kazakov
I.V., Lisovenko A.S., Bodensteiner M., Scheer M., Inorg. Chem. 2011, 50, 9039–9044. Lisovenko
A.S., Timoshkin, A.Y., Russ. J. Gen. Chem. 2011, 81, 831–839. Kazakov I.V., Timoshkin, A.Y., Russ.
J. Inorg. Chem. 2012, 57, 557–563. Lisovenko A.S., Timoshkin, A.Y., Russ. Chem. Bull. 2012, 61,
897-905.
Oral presentation - B03
Multiply Boron-Nitrogen Doped Hexi-peri-hexabenzocoronene
Holger F. Bettinger
holger.bettinger@uni-tuebingen.de
Institut für Organische Chemie, Universität Tübingen
Auf der Morgenstelle 18, 72076 Tübingen, Germany
BN substitution is an attractive means of changing electronic properties of polycyclic
aromatic hydrocarbons (PAH) without changing the molecular and crystal structure.
Hexa-peri-hexabenzocoronene (HBC), a representative nanographene molecule,1 is
related to its B3N3 derivative, BN-HBC, by substitution of the central aromatic
benzene ring by an isoelectronic borazine (“inorganic benzene”) ring. Here we show
how BN-HBC can be synthesized and isolated.2 We discuss the usefulness of the
partially hydrogenated derivatives (1 and 2) as possible precursors to BN-HBC.
References:
1. a) L. Chen, Y. Hernandez, X. Feng, K. Müllen Angew. Chem. Int. Ed. 2012, 51, 7640; b) H. Seyler,
B. Purushothaman, D.J. Jones, A. B. Holmes, W. W. H. Wong Pure Appl. Chem. 2012, 84, 1047.
2. M. Krieg, F. Reicherter, P. Haiss, M. Ströbele, K. Eichele, M.-J. Treanor, R. Schaub, H. F. Bettinger
Angew. Chem. Int. Ed. 2015, accepted for publication; (DOI: 10.1002/anie.201412165).
Oral presentation - B04
Main group metal complexes containing hybrid amino/guanidinate
(1- or 2-) ligands
Jana Nevoralova, Emilie Riemlova, Zdenka Ruzickova, Tomas Chlupaty, Ales
Ruzicka*
ales.ruzicka@upce.cz
Department of General and Inorganic Chemistry
Faculty of Chemical Technology, University of Pardubice, Studentska 573, CZ-532
10, Pardubice, Czech Republic
Stabilization of unusual[1], generally lower, oxidation states of metals in its complexes
containing amidinate/guanidinate ligands opened new areas in various catalyzed
organic chemistry transformations[1-3] Similarly applications of these complexes as
precursors for preparation of new materials is known.[4] The essential step in synthesis
of metal amidinates/guanidinates is the preparation of lithium amidinate/guanidinate
or amidine/guanidine precursors, which in contrary to the target compounds are only
rarely described in the literature.[5] Synthesis and structure of various kinds hybrid
amidinate/guanidinate lithium, dilithium and group 14 complexes will be presented
along with the reactivity of these compounds with different metal halides and amides.
Figure 1. Hybrid amino-guanidinato complex
Acknowledgements: The financial support of the Czech Science Foundation (Project no.
P207/12/0223) is gratefully acknowledged.
References:
[1] for example: (a) C. Jones, Coord. Chem. Rev., 2010, 254, 1273; (b) S.S. Sen, S. Khan, S.
Nagendran, H.W. Roesky, Acc. Chem. Res., 2012, 45, 578; (c) S. Inoue, J. D. Epping, E. Irran, M.
Driess, J. Am. Chem. Soc., 2011, 133, 1 (d) T. Chlupatý, Z. Padělková, A. yčka, J. Brus, A
Růžička, Dalton Trans., 2012, 41, 5010.
[2] F. T. Edelmann, Chem. Soc. Rev., 2009, 38, 2253; (b) S. Collins, Coord. Chem. Rev., 2011, 255,
118.
[3] for example see: (a) Z.-T. Yu, Y.-J Yuan, J.-G. Cai, Z.-G. Zou, Chem. Eur. J., 2013, 19, 1303; (b) J.
Kratsch, M. Kuzdrowska, M. Schmid, N. Kazeminejad, C. Kaub, P. Oña-Burgos, S.M. Guillaume, ,
P.W. Roesky, Organometallics, 2013, 32, 1230.
[4] for example: M. Krasnopolski, C. G. Hrib, R.W. Seidel, M. Winter, H.-W. Becker, D. Rogalla, R.A.
Fischer, F.T. Edelmann, A. Devi, Inorg. Chem., 2013, 52, 286.
[5] T. Chlupaty, R. Olejnik, A. Ruzicka, In: F.L. Tabarés, Ed., Lithium: Technology, Performance and
Safety, Chapter 4, Nova Science Publishers, Inc., Hauppauge NY, 2013.
Oral presentation - B05
Chalcogen Macrocycles Incorporating P2N2 Rings and Coinage
Metals
T. Chivers* (a), R. Thirumoorthi (a), A Nordheider (b), K. Hüll (b), K. S. Athukorala
Arachchige (b), A.M.Z. Slawin (b) and JD Woollins (b)
chivers@ucalgary.ca
a) Department of Chemistry, University of Calgary, Calgary, AB, Canada T2N 1N4;
b) Department of Chemistry, University of St Andrews, St Andrews,
University of Calgary, Calgary, AB, Canada T2N 1N4
Cyclo-P2N2-supported chalcogen macrocycles 1S and 1Se are formed upon twoelectron oxidation of the dianions [E(NtBu)P(µ-NtBu)2P(NtBu)E]2- (E = S, Se) with
iodine.1 With a view to incorporating coinage metals into these macrocycles, the
metathetical reactions of these dianions with M(I) reagents (M = Ag, Au) were found
to produce the trimeric and tetrameric macrocycles 2 and 3, embodying the
monoprotonated ligand [Se(NtBu)P(µ-NtBu)2P(HNtBu)Se]- and the intriguing ladder
complex 4, which features both monoanionic and dianionic ligands (E = S).2 The
formation and structures of 2-4 will be discussed.
References:
[1] A. Nordheider, T. Chivers, R. Thirumorthi, I. Vargas-Baca, J. D. Woollins, Chem. Commun. 2012,
48, 6346.
[2] A. Nordheider, K. Hüll, K. S. Athukorala Arachchige, A. M. Z. Slawin, J. D. Woollins, R.
Thirumoorthi, T. Chivers, Dalton Trans. 2015, 44, 5338.
Oral presentation - B06
Synthesis and Properties of Hypervalent Sulfur Radicals
Yohsuke Yamamoto1,* Yasuyuki Imada1, Kukita Tomomi1, Nakano Hideyuki2,
Furukawa Ko3, Kishi Ryohei4, Nakano Masayoshi4, Maruyama Hitoshi5, Nakamoto
Masaaki5, Sekiguchi Akira5
yyama@sci.hiroshima-u.ac.jp
Department of Chemistry, Graduate School of Science, Hiroshima University
1-3-1 Kagamiyama, Higashi-Hiroshima 739-8526, Japan
Hypervalent sulfur radicals (sulfuranyl radicals) have nine formal valence electrons in
the sulfur atom, and are considered to be intermediates in bimolecular homolytic
substitution (SH2) reactions. Although several sulfuranyl radicals have been observed
by ESR or UV-vis spectroscopies, they are elusive species and have not been
structurally characterized by X-ray analysis. In 1986, Martin et al. reported thermally
stable sulfuranyl radical 1 stabilized by a tridentate ligand.[1] Although the sulfuranyl
radical was reported to be persistent in solution, it existed in equilibrium with the
dimers, and had not been isolated and structurally characterized by X-ray analysis.
We envisioned that if the CF3 groups can be replaced by sterically hindered C2F5
groups, dimerization can be inhibited due to the steric hindrance and a sulfuranyl
radical can be isolated as a stable monomer, thereby allowing structural
characterization. Then, we prepared a new tridentate ligand precursor with C2F5
groups and sulfuranyl radical 2 as a monomer. X-ray crystallography, ESR
spectroscopy, and DFT calculation reveal the three- coordinated hypervalent structure
of 2. The corresponding hypervalent selenium radical is also isolated and
characterized. Properties and application of 2 will be discussed.
References:
[1] Perkins, C. W.; Clarkson, R. B.; Martin, J. C. J. Am. Chem. Soc.1986, 108, 3206-3210.
Oral presentation - B07
Synthesis and Characterization of Sulfur-Nitrogen π-Heterocyclic
Radical-Anion Salts with Sandwich Organometallic Cations
Nikolay A. Semenov, Nikolay A. Pushkarevsky, Lidia S. Konstantinova, Sergey N.
Konchenko, Oleg A. Rakitin, Rüdiger Mews, J. Derek Woollins, Andrey V. Zibarev*
zibarev@nioch.nsc.ru
Institute of Organic Chemistry, Russian Academy of Sciences
630090 Novosibirsk, Russia
Various new syntheses of inorganic ring systems such as [1,2,5]thiadiazolo[3,4c][1,2,5]thiadiazole (1), its Se congeners and related sulfur/selenium-nitrogen πheterocycles including (aza) benzo-fused ones were performed. Interaction of S
derivatives with sandwich organometallics MAr2(M = Cr, Mo) and MCp2(M = Co,
Cr) gave sulfur-nitrogen π-heterocyclic radical-anion (RA, S = 1/2) salts with
corresponding cations [MAr2]+ and [MCp2]+. The cations were diamagnetic
([CoCp2]+, S = 0) or paramagnetic ([CrCp*2]+, S = 3/2; [CrTol2]+, S = 1/2; and
[MoMes2]+, S = 1/2) providing homospin or heterospin salts, respectively. The
representative examples are given below. Studying Se congeners is in progress. All
salts synthesized were characterized by single-crystal X-ray diffraction (XRD) in
combination with solid-state and solution EPR. Their magnetic properties were
studied by SQUID magnetometry in temperature range 2-300 K in combination with
quantum chemical calculations. The salts revealed complex magnetic structures
dominated by antiferromagnetic exchange interactions. At the same time, the presence
of weak ferromagnetic interactions in the heterospin salts was also recognized.
Figure 1. Synthesis and XRD structures of the title salts.
Acknowledgements: The authors are grateful to the Leverhulme Trust (IN 2012-094) and Russian
Foundation for Basic Research (13-03-00072) for financial support.
References:
Lonchakov, A. V.; Rakitin, O. A.; Gritsan, N. P.; Zibarev, A. V. Molecules 2013, 18, 9850–9900 (and
references therein).
Oral presentation - B08
The Supramolecular Chemistry of Iso-Tellurazole N-Oxides
Peter C. Ho, Patrick Szydlowski, Jocelyn Sinclair, Phillip J. W. Elder, Joachim Kübel,
Chris Gendy, Lucia M. Lee, Ignacio Vargas-Baca*
vargas@chemistry.mcmaster.ca
Department of Chemistry and Chemical Biology, McMaster University
1280 Main Street West, Hamilton, Ontario, Canada L8S 4M1
Molecules that contain the heaviest chalcogens (Se, Te) often produce crystals which
feature supramolecular association.[1] For example, an iso-selenazole N-oxide forms a
centrosymmetric dimer through a pair of Se…O contacts that are shorter than the sum
of van der Waals radii.[2] In contrast, a tellurium analogue assembles an intriguing
annular tetramer.[3] Our recent investigations of these systems have revealed a variety
of new supramolecular aggregates built from iso-tellurazole N-oxides that include
hexameric rings and polymers (Figure 1). VT NMR spectroscopy demonstrated that
the tetra- and hexamers are persistent in solution and exist in equilibrium. These selfassembled structures behave as actual macrocyles that are able to form coordination
complexes with transition metal ions and act as fullerene receptors.
Figure 1. Supramolecular species derived from an iso-tellurazole N-oxide.
Acknowledgements: The support of the NSERC Canada is gratefully acknowledged. Part of this work
was made possible by the facilities of the Shared Hierarchical Academic Research Computing Network
(SHARCNET: www.sharcnet.ca) and Compute/Calcul Canada.
References:
[1] A. F. Cozzolino, P. J. W. Elder, I. Vargas-Baca, Coord. Chem. Rev. 2011, 255, 1426–1438.
[2] K. Shimada, A. Moro-oka, A. Maruyama, H. Fujisawa, T. Saito, R. Kawamura, H. Kogawa, M.
Sakuraba, Y. Takata, S. Aoyagi, Y. Takikawa, C. Kabuto, Bull. Chem. Soc. Jpn. 2007, 80, 567‑577.
[3] J. Kübel, P. J. W. Elder, H. A. Jenkins and I. Vargas-Baca, Dalton Trans. 2010, 39, 11126-11128.
Oral presentation - B09
Mixed d-/f-Metal Polypnictide Complexes
Sergey N. Konchenko*, Manfred Scheer, Peter Roesky
konch@niic.nsc.ru
Nikolaev Institute of Inorganic Chemistry SB RAS
Prosp. Lavrentieva 3, RF-630090, Novosibirsk
The presentation is devoted to collation of recent advances in the field of polypnictide
molecular f-metal and mixed d-/f-metal complexes. It is based on summarizing of
results of the long-term collaboration between research groups of the authors, and
focused on the study of reactivity of Ln(II) compounds towards a variety of
polypnictide transition metal complexes.[1] The chemistry can be basically described
as one- or two-electron reduction of polypnictide transition metal complexes causing
different types of the polypnictide unit transformation inside the coordination sphere
of metals, and formation of the mixed d-/f-metal complexes. Some examples of which
are shown below (Fig. 1).
Figure 1. Reactions of Cp*2Sm(THF)2 with (i) Cp*FeP5 and (ii) [Cp‴CoP2]2. Alkyl
substituents are omitted for clarity.
Acknowledgements: This work was supported by the Deutsche Forschungsgemeinschaft (DFG), the
Russian Foundation for Basic Research (RFBR), the Russian Ministry of Education and Science, and
the Landesstiftung Baden-Württemberg GmbH.
References:
[1] (a) T. Li, N. Arleth, M.T. Gamer, R. Koeppe, T. Augenstein, F. Dielmann, M. Scheer, S.N.
Konchenko, P.W. Roesky, Inorg. Chem., 2013, 52, 14231; (b) T. Li, M.T. Gamer, M. Scheer, S.N.
Konchenko, P.W. Roesky, Chem. Commun., 2013, 49, 2183; (c) T. Li, J. Wiecko, N.A. Pushkarevsky,
M.T. Gamer, R. Koeppe, M. Scheer, S.N. Konchenko, P.W. Roesky, Angew. Chem., Int. Ed. Engl.,
2011, 50, 9491; (d) S.N. Konchenko, N.A. Pushkarevsky, M.T. Gamer, R. Koeppe, H. Schnoeckel, P.
Roesky, J. Am. Chem. Soc., 2009, 131, 5740.
Oral presentation - B10
Phosphorus, Arsenic and Antimony Ligands in Lanthanide
Molecular Nanomagnets
Thomas Pugh and Richard A. Layfield*
Richard.Layfield@manchester.ac.uk
School of Chemistry
The University of Manchester, Oxford Road, Manchester, M13 9PL, U.K.
Rare earth metal compounds containing soft heteroatom donor ligands have attracted
considerable interest in recent years. The combination of M3+ cations with heavy pblock donor atoms results in a so-called hard-soft "mismatch"[1] that can lead to
unusual bonding properties and to distinct reactivity. Within this context, rare earth
complexes of anionic phosphorus donor ligands have been extensively studied. Some
analogous chemistry with anionic arsenic ligands is known, but such compounds are
still very rare. The use of P- and As-donor ligands in the design of lanthanide singlemolecule magnets (SMMs) is, however, entirely unknown.[2,3] In this lecture, the
dynamic magnetic properties of a series of dysprosium ring systems with phosphide,
phosphinidene, arsenide and arsinidene ligands (Figure 1) will be described.[4-6] The
experimental studies are complemented by ab initio calculations, which have enabled
us to construct a model for the magnetic anisotropy and magnetization relaxation
mechanisms in our SMMs. The theoretical model also provides insight into how
SMMs with larger anisotropy barriers may be designed, and selected new systems
with antimony-based ligands will also be presented.[7]
Acknowledgements: Financial support from the European Research Council, the Engineering and
Physical Sciences Research Council, EU Marie Curie Actions, and the Royal Society is gratefully
acknowledged.
References:
[1] T. Li, S. Kaercher, P. W. Roesky, Chem. Soc. Rev. 2014, 43, 42.
[2] D. N. Woodruff, R. E. P. Winpenny, R. A. Layfield, Chem. Rev. 2013, 113, 5110.
[3] R. A. Layfield, Organometallics 2014, 33, 1084.
[4] T. Pugh, A. Kerridge, R. A. Layfield, Angew. Chem. Int. Ed. 2014, 54, 4255.
[5] T. Pugh. L. Ungur, F. Tuna, E. J. L. McInnes, D. Collison, L. F. Chibotaru, R. A. Layfield Nat.
Commun. 2015, accepted.
[6] T. Pugh, N. F. Chilton, R. A. Layfield, manuscript submitted.
[7] Unpublished work.
Oral presentation - B11
QUEST FOR MONOMERIC STIBINIDENES AND
BISMUTHINIDENES AS NEW LIGANDS FOR TRANSITION
METALS
Libor Dostál,* Iva Vránová
libor.dostal@upce.cz
Department of General and Inorganic Chemistry, University of Pardubice
Studentká 573, Czech Republic-53210, Pardubice
Monomeric stibinidenes and bismuthinedes remained elusive species for a long time.
We have succeeded in the isolation of the first examples using of an effective
coordination of N,C,N pincer type ligands.1 Recently, analogous stibinidenes have
been prepared by Bertrand2 and Hudnall3 using stabilization by carbene ligands. The
present studies in our labs is focused on the influence of the structure of particular
C,N-chelating ligand on the structure of antimony(I) and bismuth(I) compounds with
particular emphasis on the preparation of stibinidenes and bismuthinedes (Figure 1).
As both stibinidenes and bismuthinedes formally contain two lone pairs of electrons
on the central atom, the preliminary results of their coordination behavior towards
transition metal fragments will be discussed.
Figure 1. Structure of studied compounds
Acknowledgements: The authors thank the Grant Agency of the Czech Republic project. no. P207/1506609S.
References:
[1] Šimon, P. De Proft, F. Jambor, R. Růžička, A. Dostál, . Angew. Chem. Int. Ed. 2010, 49, 5468.
[2] Kretschmer, R.; Ruiz, D.A.; Moore, C.E.; Rheingold, A.L.; Bertrand, G. Angew. Chem. Int. Ed.
2014, 53, 8176.
[3] Dorsey, C.L.; Mushinski, R.M.; Hudnall, T.W. Chem. Eur. J. 2014, 20, 8914.
Oral presentation - B12
Iron-Catalyzed Routes to Phosphorous-Containing Rings
Rory Waterman
rory.waterman@uvm.edu
Department of Chemistry, University of Vermont
Burlington, VT 05401, USA
Transition-metal catalysts can readily convert primary phosphines to cyclo-phosphine
products. In contrast, simple iron compound such as CpFeMe(CO)2have demonstrated
the ability to reliably convert dicyclohexylphosphine (CyPH2) to P5Cy5in low but
reliable conversion where the major product is the expected diphosphine, (Cy2P)2.
This observation suggested the extrusion of a phosphinidene fragment that might be
trapped with organic substrates. Indeed, primary aryl and alkyl phosphines can be
converted to phospholes with alkynes or dienes in the presence of an iron catalyst
(eq). Mechanistic study and further synthetic efforts will be presented.
Acknowledgements: This work was supported by the U.S. National Science Foundation. RW
acknowledges fellowship support from the Alexander von Humboldt Foundation.
Oral presentation - B13
One, two, three Halogens on the Ring - on the Formation Mechanism
of N-Heterocyclic Haloboranes and Halophosphanes
Dirk Hermannsdörfer, Manuel Kaaz, Oliver Puntigam, Johannes Bender, Martin
Nieger, Dietrich Gudat*
gudat@iac.uni-stuttgart.de
Institut für Anorganische Chemie, University of Stuttgart
Pfaffenwaldring 55, GER-70550 Stuttgart
N-heterocyclic haloboranes (NHB, I) and halophosphanes (NHP, II) are important
precursors for NHC analogues and may also serve as key intermediates in syntheses
of further heterocycles. Their preparation from diazadienes is usually accomplished in
two-steps via reduction of the diazadiene by a metal and subsequent ring closing
metathesis with a suitable electrophile. In addition, also several reports on one-step
syntheses of NHPs[1] and NHBs[2] via (oxidative) cycloadditions are known.
Depending on starting materials and reaction conditions, these reactions yield either
mono-halogenated (I, II) or dihalogenated heterocycles (III, IV). Here, we report on
experimental and computational studies of the reaction mechanism of the
cycloaddition processes. Our results provide a systematic understanding of the
pathways leading to mono- and dihalogenated heterocycles, and it will be shown how
the reaction can be driven into either direction. Furthermore, syntheses of trihalogenosubstituted NHBs and NHP-NHB "adducts" V will be presented.
Figure 1. Molecular structures of NHBs and NHPs (X = Cl, Br, I, R = alkyl, aryl) and NHPNHB "adducts"
References:
[1] (a) A. M. Kibardin, I. A. Litvinov, V. A. Naumov, T. Struchkov, Y. Mikhailov, A. N. Pudovik,
Dokl. Akad. Nauk. SSSR 1988, 298, 369; (b) M. Kibardin, A. N. Pudovik, Russ. J. Gen. Chem. 1993,
63, 1687; (c) G. Reeske, A. H. Cowley, Inorg. Chem. 2007, 46, 1426; (d) J.W. Dube, G.J. Farrar, E.L.
Norton, K. L. S. Szekely, B. F. T. Cooper, C. L. B. Macdonald, Organometallics 2009, 28, 4377.
[2] (a) L. Weber, J. Förster, H.-G. Stammler, B. Neumann, Eur. J. Inorg. Chem. 2006, 5048; (b) A.
Hinchliffe, F. S. Mair, E. J. L. McInnes, R. G. Pritchard, J. E. Warren, Dalton Trans. 2008, 222.
[3] M. Kaaz, J. Bender, D. Förster, W. Frey, M. Nieger, D. Gudat, Dalton Trans. 2014, 43, 680.
Oral presentation - B14
Peri-Interactions within (Ace)Naphthyl Compounds Reloaded
Jens Beckmann
j.beckmann@uni-bremen.de
Institut für Anorganische Chemie, Universität Bremen
Leobener Str. GER-28359 Bremen
The close proximity of peri-substituents in 1,8- and 5,6-positions of naphthalene and
acenaphthene gives frequently rise to unique bond situations and codependent
reactivity. We are interested in ′through-space′ peri-interactions of
diphenylphosphino(ace)naphthyl compounds that can be either repulsive due to steric
congestion or attractive due to weak or strong bonding. The potential of selected
compounds as ligands for coinage metal salts will be also elaborated.[1-6]
References:
[1] J. Beckmann, E. Hupf, E. Lork, S. Mebs, Inorg. Chem. 2013, 52, 11881-11888.
[2] E. Hupf, E. Lork, S. Mebs, J. Beckmann, Organometallics 2014, 33, 2409-2423.
[3] E. Hupf, E. ork, S. Mebs, . Chęcińska, J. Beckmann, Organometallics 2014, 33, 7247-7259.
[4] E. Hupf, E. Lork, S. Mebs,J. Beckmann, Inorg. Chem. 2015, 54, 1847-1859.
[ ] A. Nordheider, E. Hupf, B. A. Chalmers, F. R. night, M. Bühl, S. Mebs, . Chęcińska, E. ork, P.
Sanz Camacho,S. E. Ashbrook, K. S. Athukorala Arachchige, D. B. Cordes, A. M. Z. Slawin, J.
Beckmann, J. D. Woollins, Inorg. Chem. 2015, 54, 2435-2446.
[6] J. Brünig, E. Hupf, E. Lork, S. Mebs J. Beckmann, Dalton Trans. 2015, DOI:10.1039/C5DT00588.
Oral presentation - B15
Synthesis and reactivity of phosphinidene boranes
Amy N. Price, Michael J. Cowley*
michael.cowley@ed.ac.uk
School of Chemistry, University of Edinburgh
Joseph Black Building, West Mains Road, Edinburgh, EH9 3FJ, United Kingdom
Phosphinidene boranes, RP=BR, are the heavier homologues of the widely studied
imino-boranes, RN=BR. In contrast to the imino-boranes, few examples are known
and those that do exist are generally stabilized by coordination of Lewis acids or bases
to the phosphorus or boron centres respectively.[1–3] Nevertheless, the reactivity of the
as-yet-unknown uncoordinated phosphinidene-boranes, especially given recent
progress in the chemistry of the isoelectronic group 14 alkyne analogues, is of high
interest. We have recently embarked upon a project designed to prepare the first
acid/base-free phosphindene boranes, and here report some preliminary results,
including a new high-yielding route to base-stabilised phosphinidene boranes. For
example, treatment of the functional phosphino-borane 1 with a range of Lewis bases
(e.g. DMAP) results in the formation of base-stabilized phosphinidene boranes such
as 2, whilst reactions with larger NHCs lead to desilylation to form 3. We will present
details of the synthesis, structure and reactivity of these compounds and related
species.
Figure 1. Reactivity of the functional phosphinoborane 1.
Acknowledgements: We gratefully acknowledge the University of Edinburgh and the European
commission (Marie Curie CIG to MC) for funding.
References:
[1] G. Linti, H. Nöth, K. Polborn, R. T. Paine, Angew. Chem. Int. Ed. Engl. 1990, 29, 682–684.
[2] E. Rivard, W. A. Merrill, J. C. Fettinger, P. P. Power, Chem. Commun. 2006, 3800–3802.
[3] E. Rivard, W. A. Merrill, J. C. Fettinger, R. Wolf, G. H. Spikes, P. P. Power, Inorg. Chem. 2007,
46, 2971–2978.
Oral presentation - B16
Unconventional Ring Sizes with Noninnocent Ligand Components
Wolfgang Kaim
kaim@iac.uni-stuttgart.de
Institut für Anorganische Chemie, Universität Stuttgart
Pfaffenwaldring 55, D-70550 Stuttgart, Germany
The vast majority of cyclic molecular and coordination compounds with redox-active,
i.e. noninnocently behaving ligands involves five-membered (chelate) rings. orthoQuinone, dithiolene and α-diimine complexes are among the best known examples.1
(Formula 1) Only recently have six-membered such rings with a variable number of
heteroatoms been reported,2-4 including those with “hidden noninnocence”.2 (Formula
2) The requirement for such unusual arrangements and new examples5 for fourmembered ring species will be presented and their noninnocence will be discussed.
(Formula 3)
References:
1 W. Kaim, Inorg. Chem. 2011, 50, 9737-9914.
2 M. M. Khusniyarov, E. Bill, T. Weyhermüller, E. Bothe, K. Wieghardt, Angew. Chem. 2011, 123,
1690-1693; Angew. Chem. Int. Ed. 2011, 50, 1652-1655.
3 H. Agarwala, T. M. Scherer, S. M. Mobin, W. Kaim, G. K. Lahiri, Dalton Trans. 2014, 43, 39393948.
4 M.-C. Chang, T. Dann, D. P. Day, M. Lutz, G. G. Wildgoose, E. Otten, Angew. Chem. 2014, 126,
4202-4206; Angew. Chem. Int. Ed. 2014, 53, 4118-4122.
5 F. Ehret, M. Bubrin, S. Zalis, W. Kaim, Angew. Chem. 2013, 125, 4771-4773; Angew. Chem. Int.
Ed. 2013, 52, 4673-4675.
6 F. Ehret, M. Bubrin, S. Zális, W. Kaim, Z. Allg. Anorg. Chem. 2014, 640, 2781-2787.
Oral presentation - B17
The sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienides
derivatives: synthesis and coordination properties
Ilya A. Bezkishko(a)*, Lilia R. Kochetkova(a), Vasily A. Miluykov(a), Olga N.
Kataeva(a), Oleg G. Sinyashin (b)
bezkishko@gmail.com
(a) A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific
Center, Russian Academy of Sciences; Arbuzov str. 8, 420088, Russia, Kazan
(b) Leipzig University, Institute of Inorganic Chemistry
The 1,2-diphosphacyclopentadienide anion, an isolobal analogue of the Cp- and
pyrazolate anion, has an significant interest as ligand in coordination chemistry due to
the possibility of realizing various coordination modes with metal atoms[1]. We have
found a new convenient synthesis of sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienide and studied their coordination properties. The coordination mode
of 1,2-diphosphacyclopenatdienide to metal in obtained complexes determine their
magnetic properties.
Acknowledgements: This work was supported by the Russian Science Foundation (grant №1 -1300589).
References:
[1] I.A. Bezkishko, A.A. Zagidullin, V.A. Milyukov, O.G. Sinyashin, Russ. Chem. Rev., 2014, 83(6),
555
Oral presentation - B18
Laterally-Functionalized Phospholes – Versatile Building Blocks for
π-Conjugated Materials
Xiaoming He, Thomas Wang, Thomas Baumgartner*
thomas.baumgartner@ucalgary.ca
Department of Chemistry and Centre for Advanced Solar Materials, University of
Calgary
2500 University Drive NW, Calgary, AB T2N 1N4, Canada
The design of luminescent materials with well-organized one- or two-dimensional
structures is gaining considerable importance for the rapidly evolving field of organic
electronics. In this context, the incorporation of organophosphorus ring systems into
π-conjugated materials has recently created a promising new avenue for efficiently
engineering the optoelectronic properties at the molecular level.[1,2] This presentation
will highlight the synthesis, properties, and practical applications of new functional
phospholes that can easily be converted into luminescent soft materials via lateral
functionalization at the phosphorus center. Depending on the specific architecture of
the conjugated scaffold, the self-assembly properties of the materials can be turned
on/off. The overall morphology of the obtained nano-/microstructures can furthermore
be addressed by the degree of π-conjugation in the head group. Moreover, the
functional properties of the system can also effectively be tuned by variation of the
pendant group.
References:
[1] T. Baumgartner, Acc. Chem. Res. 2014, 47, 1613-1622.
[2] Z. Wang, T. Baumgartner, Chem. Rec. 2015, 15, 199-217.
Oral presentation - B19
From cyclic and polycyclic alkoxoaluminium hydrides to alumina
composites with nano- and micro-meter rings and cages
Michael Veith, Ali Awadelkareem, Hakima Smail-Bubel, Marina Martinez-Miró,
Cenk Aktas, Karin Kiefer
michael.veith@inm-gmbh.de
Universität des Saarlandes und Leibniz-Institut für Neue Materialien
Campus D2.2, GER-66123 Saarbrücken
Alkoxoalanes of the general formula (RO)xAlH3-x may form different oligomers
depending on the organic substituent R. While with R= tert-butyl the compound
[(CH3)3C-O-AlH2]2 (1) is dimeric with a simple Al2O2-ring, the cyclo-pentyl
derivatives show a large variety of polycyclic structures of which [H6Al4(O-C5H9)6]
and [H16Al8(O-C5H9)8] are cited as examples. Treating 1 with diphenyl-silane-diol
Ph2Si(OH)2 and subsequently with metal acetylacetonates (acac)2M(H2O)2 (M= Mg,
Fe, Co, Ni) leads to new polycycles with disiloxane and acetylacetonate chelates of
the general formula [(acac)2Al(O-SiPh2-O-SiPh2-O)]2M(H2O)2 with M= Mg, Fe, Co,
Ni. These new molecular alumosilikates display two acetyl-acetonate ligands at the
aluminum atoms as well as two disilatrioxy chains linking the aluminum atoms to
obtain a twelve-membered (Al-O-Si-O-Si-O)2 cycle, in the centre of which the
divalent metal atoms are linked through four oxygen atoms of the cycle. Thermolysis
of 1 at moderate temperatures in the gas phase produces Al/Al2O3-composites which
adopt different nano-structures depending on the pressure and temperature. We have
recently been able to analyze the three dimensional structures of these composites by
FIB-microscopy in detail and could establish ring and cage structures composed of
Al/Al2O3 with reproducible nano- and mico-meter dimensions. The holes and surfaces
of these structures can be used for storage of small molecules or as a sort of scaffold
for living cells. In this second application either adhesion or rejection for the cell may
be triggered. With certain surface modifications even preferential cell growth is
obtained.1
References:
1) K. Kiefer, J. Lee, A. Haidar, M. Martinez-Miró, C.K. Akkan, M. Veith, O.C. Aktas, H. AbdulKhaliq, Nanotechnology, 2014, 25, 495101.
Oral presentation - B20
A WORLD OF DIFFERENCE – ALKALI METAL ORGANIC
FRAMEWORKS FROM AMMONIA
Dietmar Stalke
dstalke@chemie.uni-goettingen.de
Institut für Anorganische Chemie der Georg-August Universität Göttingen
Tammannstr. 4, 37077 Göttingen, Germany
Layered structures and intercalation compounds play an outstanding role in materials
science. Most prominent are graphite intercalation compounds due to their use in
energy storage via Li-ion batteries. We envisage self-assemblies of charged
supramolecular sandwich structures to form by polycyclic carbanions and alkali metal
cations to represent structural motifs of charged anode materials in prospective
rechargeable batteries. A small flat and charged building block is the indenyl anion
[Ind]- and an advantageous donor base for this endeavour is ammonia. Both ammines,
[Li(NH3)4][Ind] and [Na(NH3)4][Ind], contain a cation coordinated by four ammonia
molecules. While the first shows the anticipated tetrahedral coordination, in the
second cation the metal is unexpectedly square planar coordinated. The solvent
separated ion pair forms a rippled layer structure of alternating planar Na(NH3)4+
cations and indenyl carbanions, attributed to NH3Lp hydrogen bonds (Fig. 1).[1] Those
hydrogen bonds are a robust structure-determining feature, studied by means of
experimental and theoretical charge density studies. The density distribution in
[CpNa(NH3)3] can be considered a spectacular illustration of the structuredetermining strength of intermolecular interactions; the N–HLπ interactions are strong
enough to compete with the polarising effect of the sodium cation towards the density
of the cyclopentadienide ring.[2] We have shown recently that addition of ammonia to
THF generates lithocene or even naked Cp anions.[3] The strong donating and deaggregating properties of ammonia observed herein are the most likely reason for the
high reaction rate of many organometallics in liquid ammonia. The use of ammonia
can be the key for reactions with a high potential barrier caused by steric repulsion.[4]
Figure 1. [Na(NH3)4][Ind]
References:
[1] Michel R., Nack T., Neufeld R., Dieterich J. M., Mata R. A. and Stalke D., Angew. Chem. 2013,
125, 762-766; Angew. Chem. Int. Ed. 2013, 52, 734-738.
[2] Hey J., Andrada D. M., Michel R., Mata R. A. and Stalke D., Angew. Chem. 2013, 125, 1055510559; Angew. Chem. Int. Ed. 2013, 52, 10365-10369.
[3] Michel R., Herbst-Irmer R. and Stalke, D., Organometallics 2010, 29, 6169-6171.
[4] Michel R., Herbst-Irmer R. and Stalke, D., Organometallics 2011, 30, 6169-6171.
Oral presentation - B21
Coordination Polymers from Main Group Ring Compounds
Saturday Amedu Okeh, René T. Boeré*
boere@uleth.ca
Department of Chemistry and Biochemistry, University of Lethbridge
4401 University Dr, Lethbridge, AB, Canada T1K 3M4
Coordination polymers built from bridging organic ligands are well established in the
literature and have been developed for numerous applications. Much less has been
reported on using main group ring compounds, which provide a rich opportunity for
redox activity of the ligands.[1] Herein we report on novel results using 4,7disubstituted-2,1,3-benzothiadiazoles as bridging ligands for coordination polymers.
The ligands (nitrile, ester and carboxylic acid functional groups) are prepared
according to literature procedures (see Figure).[2] The synthesis, structures and
properties of a number of coordination polymers of Ag(I) will be presented.
Figure 1. Synthesis of 4,7-disubstituted-2,1,3-benzothiadiazole ligands (above), displacement
ellipsoids plot of the asymmetric unit in [Ag(DCBTD)]BF4 (below).
References:
[1]L. R. MacGilivray, Ed., Metal-Organic Frameworks: Design and Application; Wiley: Chichester,
2010; p. 165-192.
[2] (a) K. Pilgram, R. D. Skiles, J. Heterocycl. Chem., 1974, 11, 777; (b) K. Pilgram, J. Heterocycl.
Chem., 1974, 11, 834.
Oral presentation - B22
Ligand Chemistry of Stable Phosphorus(I) Compounds
Charles L. B. Macdonald*, Justin F. Binder, Ala'aeddeen Swidan, Stephanie M.
Kosnik, Bobby D. Ellis
cmacd@uwindsor.ca
Chemistry & Biochemistry
University of Windsor 401 Sunset Ave., Windsor, ON, N9B 3P4, Canada
For more than a decade, we have been investigating the chemistry of compounds
containing p-block elements in unusually low oxidation states.[1] For group 15, we
have developed convenient syntheses for compounds containing donor-stabilized P(I)
ions.[2] Many of these compounds (see Figure 1 for some structural depictions) are airand moisture-stable and some are valuable reagents for the synthesis of other stable
low-oxidation state species using ligand replacement reactions. The univalent
phosphorus atoms in such molecules resemble those of phosphanides in that they
feature two pairs of non-bonding electrons that may be suitable for binding to metals
or Lewis acids; several research groups have demonstrated that these molecules do
indeed exhibit interesting ligand chemistry.[3] Our latest results will be presented.
Figure 1. Molecular structures of some stable P(I) compounds we investigate.
Acknowledgements: We thank NSERC, CFI, and the Government of Ontario.
References:
[1](a) C. L. B. Macdonald, B. D. Ellis, A. Swidan, Encyclopedia of Inorganic and Bioinorganic
Chemistry, John Wiley & Sons, Ltd, 2012; (b) B. D. Ellis, C. L. B. Macdonald, Coord. Chem. Rev.
2007, 251, 936-973.
[2](a) B. D. Ellis, C. A. Dyker, A. Decken, C. L. B. Macdonald, Chem. Commun. 2005, 1965-1967; (b)
B. D. Ellis, C. L. B. Macdonald, Inorg. Chem. 2006, 45, 6864-6874; (c) E. L. Norton, K. L. S. Szekely,
J. W. Dube, P. G. Bomben, C. L. B. Macdonald, Inorg. Chem. 2008, 47, 1196-1203.
[3](a) J. W. Dube, C. L. B. Macdonald, P. J. Ragogna, Angew. Chem. Int. Ed. 2012, 51, 13026-13030;
(b) J. W. Dube, C. L. B. Macdonald, B. D. Ellis, P. J. Ragogna, Inorg. Chem. 2013, 52, 11438-11449;
(c) K. Schwedtmann, M. H. Holthausen, K. O. Feldmann, J. J. Weigand, Angew. Chem. Int. Ed. 2013,
52, 14204-14208; (d) S. C. Kosnik, G. J. Farrar, E. L. Norton, B. F. T. Cooper, B. D. Ellis, C. L. B.
Macdonald, Inorg. Chem. 2014, 53, 13061-13069; (e) J. F. Binder, A. Swidan, M. Tang, J. H. Nguyen,
C. L. B. Macdonald, Chem. Commun. 2015, in press.
Oral presentation - B23
THERMOCHROMIC EMISSIVE METALLACYCLES
Lescop. C.,*(a) El Sayed Moussa. M.,(a) Evariste. S.,(a) Wong. H-L.,(b) Le Bras.
L.,(c) Le Guennic. B.,(c) Costuas.
christophe.lescop@univ-rennes1.fr
(a) Phosphore et Matériaux Moléculaires, UMR 6226 CNRS-Université de Rennes 1
Campus de Beaulieu, 35042 Rennes Cedex, France
(b) Department of Chemistry, University of Hong Kong, Hong Kong, Chine
(c) Chimie Théorique et Inorganique ISCR
Thermochromic luminescent derivatives constitute a peculiar class of emissive
materials whose emission varies with temperature.[1] To date, the most remarquable
class of such derivatives is mostly based on Cu4I4 cubane cores.[1c-e] Using a very
general supramolecular chemistry synthetic approach previously developped in our
group,[2] a new series of polymetallic Cu(I) metallacycles Cu n (n= , , 12, ∞) has
been recently obtained. Their syntheses, solid state caracterizations will be presented
together with their themochromic emissive behaviors and TD-DFT calculations aimed
to understand the electronic structure of these derivatives.
Acknowledgements: The ANR (France) and the RGC (Hong Kong) (projet ANR-RGC Int. POPTOELECTR-MOLMAT), the Humboldt Foundation, the Ministère de la Recherche et de
l’Enseignement Supérieur and the CNRS are thanked.
References:
[1] a) J. Feng, K. J. Tian, D. H. Hu, S. Q. Wang, S. Y. Li, Y. Zeng, Y. Li, G. Q. Yang, Angew. Chem.
Int. Ed. 2011, 50, 8072; b) F. M. Ye, C. F. Wu, Y. H. Jin, Y. H. Chan, X. J. Zhang, D. T. Chiu, J. Am.
Chem. Soc. 2011, 133, 8146; c) H.D. Hardt, A.Z. Pierre, Z. Anorg. Allg. Chem., 1973, 402,107; d) S.
Perruchas, C. Tard, X. F. Le Goff, A. Fargues, A. Garcia, S. Kahlal, J-Y. Saillard, T. Gacoin, J. P.
Boilot, Inorg. Chem, 2011, 50, 10682; e) D. Sun, S. Yuan, H. Wang, H-F. Lu, S-Y. Feng, D-F. Sun,
Chem. Commun., 2013, 49, 6152; f) K. Miyata, Y. Konno, T. Nakanishi, A. Kobayashi, M. Kato, K.
Fushimi, Y. Hasegawa, Angew. Chem. Int. Ed. 2013, 52, 6413.
[2] a) B. Nohra, S. Graule, C. Lescop, R. Réau, J. Am. Chem. Soc. 2006, 128, 3520; b) B. Nohra, Y.
Yao, C. Lescop, R. Réau, Angew. Chem. Int. Ed., 2007, 46, 8242; c) Y. Yao, W. Shen, B. Nohra, C.
Lescop, R. Réau, Chem. Eur. J. 2010, 16, 7143; d) V. Vreshch, W. Shen, B. Nohra, S-K Yip, V.W-W.
Yam, C. Lescop, R. Réau, Chem. Eur. J., 2012, 2, 466; e) M. El Sayed Moussa, K. Guillois, W. Shen,
R. Réau,J. Crassous, C. Lescop, Chem. Eur. J., 2014, 20, 14853.
Oral presentation - B24
Paving the Way to Novel Phosphorus-based Architectures: a Noncatalyzed Protocol to Access Fused Heterocycles
Carlos Romero-Nieto, Alicia ópez-Andarias, Carolina Egler-Lucas, Florian Gebert,
Jens-Peter Neus, Oliver Pilgram
Carlos.romero.nieto@oci.uni-heidelberg.de
Organisch-Chemisches Institut, University of Heidelberg
Im Neuenheimer Feld 270, Room 270a, GER-69120, Heidelberg
Opening up new horizons into materials science requires the development of novel
architectures. To that end, phosphorus heterocycles provide a wide set of unique
possibilities. Thus, the singular hybridization of phosphorus centers enables a series
of reversible post-functionalization reactions.[1] The latter allow: a) tailoring the
optoelectronic properties to specific applications and, b) adjusting the intermolecular
interactions to access intriguing phenomena such as piezochromism,[2]
thermochromism[3] and liquid crystallinity[3] among others. To exploit the
aforementioned features into materials science, a great deal of research efforts has
been invested in providing new synthetic routes to prepare phosphorus heterocycles.[4]
Currently, however, synthetic protocols to access π-extended phosphorus-based
structures still remain scarce. In this communication, I present a new non-catalyzed
synthetic protocol to obtain novel, fused phosphorus heterocycles. The scope of this
reaction reveals a great potential to access superior π-extended systems. Postfunctionalization reactions either at the main scaffold or at the phosphorus center
bring about a series of unusual optoelectronic properties. Altogether, our phosphorusbased architectures introduce new opportunities into the field of functional materials.
Acknowledgements: Financial support by the Fonds der Chemischen Industrie, Germany, is gratefully
acknowledged. We also thank the Organisch-Chemisches Institut, Universität Heidelberg, Germany,
for its support.
References:
[1] T. Baumgartner, Acc. Chem. Res., 2014, 47, 1613-1622.
[2] Y. Ren, W. H. Kan, M. A. Henderson, P. G. Bomben, C. P. Berlinguette, V. Thangadurai, T.
Baumgartner, J. Am. Chem. Soc. 2011, 133, 17014-17026.
[3] C. Romero-Nieto, M. Marcos, S. Merino, J. Barberá, T. Baumgartner, J. Rodríguez-López, Adv.
Funct. Mater. 2011, 21, 4088-4099.
[4] (a) K. Baba, M. Tobisu, N. Chatani, Angew. Chem. Int. Ed. 2013, 52, 1-5; (b) Y. Kuninobu, T.
Yoshida, K. Takai, J. Org. Chem. 2011, 76, 7370-7376; (c) S. Furukawa, S. Haga, J. Kobayashi, T.
Kawashima, Org. Lett. 2014, 16, 3228-3231.
Oral presentation - B25
Photoinduced Rearrangement of Acylcyclopolysilanes
Harald Stueger, Michael Haas, Bernd Hasken, Roland Fischer, Michaela Flock,
Martin Rausch, Lukas Schuh, Ana Torvisco
harald.stueger@tugraz.at
Institute of Inorganic Chemistry, Graz University of Technology
Stremayrgasse 9, 8010 Graz, Austria
Only selected examples of stable Si=C bonded species with Si-Si bonds and the
unsaturated silicon atom incorporated into cyclic structures have been synthesized so
far.[1] Thus, previously unknown acylcyclohexasilanes (Me3Si)2Si6Me8(Me3Si)COR
(1; R = alkyl, aryl) have been synthesized and their photochemical rearrangement
reactions have been studied.[2] When photolyzed with λ > 300 nm radiation alkyl
substituted type 1 compounds showed Brook type 1,3-Si→O migration reactions to
generate the cyclohexasilanes 2 with exocyclic Si=C bonds along with smaller
amounts of the ring enlarged species 3 with endocyclic Si=C double bonds. While 2
was stable enough to allow characterization by NMR and UV absorption spectroscopy
the less stable products 3 could only be observed in form of their methanol adducts.
With an o-tolyl-group attached to the carbonyl C atom under the same conditions 1
exclusively underwent ring scission adjacent to the Si-C=O moiety followed by 1,3Si→O migration of the resulting terminal SiMe2group to give the endocyclic product
3 with remarkable selectivity, which could be isolated and fully characterized.
Figure 1. Photochemical rearrangement of acylcyclohexasilanes.
References:
[1] H. Ottosson, A. M. Eklöf, Coord. Chem. Rev. 2008, 252, 1287.
[2] (a) H. Stueger, B. Hasken, M. Haas, M. Rausch, R. Fischer, A.Torvisco, Organometallics 2014, 33,
231. (b) M. Haas, R. Fischer, L. Schuh, R. Saf, A. Torvisco, H. Stueger, Eur. J. Inorg. Chem. 2015,
997.
Oral presentation - B26
Cyclodiphosphazanes in Metal Organic Frameworks
Maravanji S. Balakrishna Mujahuddin M. Siddiqui Guddekoppa S. Anantnag
krishna@chem.iitb.ac.in
Department of Chemistry
Phosphorus Laboratory, Indian Institute of Technology Bombay, Powai, Mumbai
400076, India
The coordination chemistry of cyclodiphosphazanes or diazadiphosphetidines has
been extensively studied in recent years and this is mainly due to the generation of
several interesting derivatives with donor functionalities. However, the utility of
either bisphosphanes or cyclodiphosphazanes in designing homolyptic metal organic
frameworks is scarce. This may be due to the non-availability of suitable linkers with
rigid frameworks (such as 4,4’-bipyridine) as the pyramidal geometry at the
phosphorus atom and free rotation about the P–C bonds allow a range of accessible
orientations of lone pairs bringing a disambiguity in the coordination behavior. In this
context, we have designed structurally more rigid cyclodiphosphazanes and explored
their rich transition metal chemistry. In this talk, a few such systems will be discussed
Figure 1: Copper(I)-Cyclodiphosphazanes Complexes with Sodalite and Dimonodoid
Structures
Acknowledgements: This work is supported by a grant SR/S1/IC-17/2014 from De-partment of
Science and Technology (DST), New Delhi, India. We are thankful to Prof. Joel T. Mague, Tulane
University, New Orleans, for X-ray structure determination.
References:
[1] M. M. Siddiqui, S. M. Mobin, I. Senkovska, S. Kaskel, M.S. Balakrishna, Chem. Commun. 2014,
50 12207-12209.
[2] M.M. Siddiqui , J. T. Mague, M. S. Balakrishna, Inorg. Chem. 2015, 54, 1200-1202.
[3] G.S. Ananthnag , J.T. Mague, M.S. Balakrishna, Dalton Trans. 2015, 44, 3785-3793.
Oral presentation - B27
Complexes Containing W≡E (E = P, As and Sb) Triple Bond as
Precursors for Linearly Coordinated EQ (Q = O, S, Se and Te)
Ligands
Gábor Balázs, Manfred Scheer
gabor.balazs@ur.de
Institute of Inorganic Chemistry, University of Regensburg
Universitätsstraße 31, GER-93053, Regensburg
The coordination chemistry of nitrogen monoxide (NO) was extensively studied in the
early 70s. This versatile ligand can adopt a wide range of bonding motifs in transition
metal complexes. In contrast, the coordination chemistry of the heavier homologues is
less studied. This is partly due to the unavailability of the free EQ (E = P, As, Sb, Bi; Q =
S, Se, Te) ligands as well as to their poor coordinating abilities. The majority of known
transition metal EQ complexes contains PQ (Q = O, S, Se) ligands that are coordinated to
three metal centers in a μ3 fashion. The synthesis of the isolable terminal pnictido
complexes [(N3N)W≡E] [N3N=N(CH2CH2NSiMe3)3; E = P, As, Sb][1] made the synthesis
of complexes containing η1-EQ ligands accessible. Our interest was oriented toward the
synthesis and reactivity studies of complexes containing linear EQ ligands. The oxidation
of [(N3N)W≡E] (E = P, As) with chalcogenes or suitable calcogene sources leads to the
formation of the corresponding [(N3N)W(η1-EQ)] complexes (Equation 1; Figure 1).[2]
Quantum chemical calculations show that the bonding in the W–E–Q unit is best
described by two polarized double bonds.[3] An overview of the reactivity of
[(N3N)W(η1-EQ)] complexes will be presented.
Figure 1. Synthesis and Molecular structure of [{(Me3SiNCH2CH2)3N}W(η1-PTe)]. H atoms
omitted for clarity.
References:
[1] a) R. R. Schrock, N. C. Zanetti, W. N. Davis Angew. Chem. Int. Ed. Engl. 1995, 34, 2044; b) M.
Scheer, J. Müller, M. Häser Angew. Chem. 1996, 108, 2637; c) G. Balázs, M. Sierka, M. Scheer
Angew. Chem. Int. Ed. 2005, 44, 4920.
[2] Balázs, G.; Green, J. C.; Scheer, M. Chem. Eur. J. 2006, 12, 8603-8608.
[3] Balázs, G.; Green, J. C.; Mingos, D. M. P. Eur. J. Inorg. Chem. 2007, 2443-2453.
Oral presentation - C01
Is Single-4-Ring the Most Basic but Elusive Secondary Building Unit
that Transforms to Larger Structures in Zinc Phosphate Chemistry?
Ramaswamy Murugavel
rmv@chem.iitb.ac.in
Indian Institute of Technology Bombay, Powai, Mumbai 400076, India
Our laboratory has been using an organophosphate monoester (ArO)P(O)(OH) (Ar =
2,6-diisopropylphenyl) as the primary building unit (PBU) to assemble polyhedral
molecules that resemble one or more zeolite secondary building units and display
various functions.1-4 The reaction of this PBU with a divalent metal ion such as Zn2+
in a donor solvent leads to the isolation of stable tetranuclear metal phosphates
[(ArO)PO3Zn(L)]4 build around a Zn4O12P4D4R SBU core. In recent times we have
unraveled that it is also possible to isolate other SBUs, starting from the same set of
reactants, but by making small variations in the reaction conditions. Now it is possible
to isolate hitherto unknown discrete D6R and D8R SBUs (which possess Zn6O18P6
and Zn8O24P8 cores, respectively) by switching the solvent from methanol to
acetonitrile and the co-ligand from DMSO to either 3-formylpyridine5 or 4cyanopyridine.6 Irrespective of the conditions employed, S4R SBUs are formed as the
initial products. By co-existence of free phosphoryl groups and coordinative
unsaturation at zinc, these S4R SBUs aggregate. The explanation for the formation of
larger SBUs such as D6R and D8R from a S4R however would need a two-stage
mechanism involving (a) side-by-side fusion of two or more S4Rs and (b) a
constructive folding to close up the double-n-ring (n = 4, 6, or 8) SBUs. One cannot
discount the possibility of misfolding in step (b), which will lead to the isolation of
polymeric chains with a staircase conformation.
Figure 1. Single-4-Ring, the basic structural unit
References:
1. Kalita, A.C.; Roch-Marchal, C.; Murugavel, R. Dalton Trans., 2013, 26, 9755.
2. Kalita, A.C.; Murugavel, R. Inorg. Chem., 2014, 53, 3345.
3. Kalita, A.C.; Gogoi, N.; Jangir, R.; Kupuswamy, S.; Walawalkar, M. G.; Murugavel, R. Inorg.
Chem., 2014, 53, 8959.
4. Kalita, A.C.; Sharma, K.; Murugavel, R. Cryst. Eng. Comm. 2014, 16, 51.
5. Gupta, S.K.; Dar, A. A.; Rajeshkumar, T.; Kuppuswamy, S.; Langley, S. K.; Murray, K. S.;
Rajaraman, G.; Murugavel, R. Dalton Trans. 2015, 44, 5587.
6. Gupta, S.K.; Kuppuswamy, S.; Walsh, J. P. S.; McInnes, E. J. L.; Murugavel, R. Dalton Trans. 2015,
44, 5961.
7. Dar, A.; Sharma, S. K. Murugavel, R. Inorg. Chem. 2015, in press.
Oral presentation - C02
NHC Ligands for Ternary Metal-Chalcogen Cluster Assembly
Mahmood Azizpoor Fard, Bahareh Khalili Najafabadi, John F. Corrigan*
corrigan@uwo.ca
Department of Chemistry, The University of Western Ontario
1151 Richmond St, London, N6A 5B7, Canada
Ligand stabilized metal-trimethylsilylchalcogenolates [LnM-ESiMe3] (L = PR3; E = S,
Se, Te; M = Cu, Ag) offer routes for the controlled formation of several ternary M-EM´ clusters when these coordination complexes are reacted with a second metal salt.
This arises from the reactivity of the chalcogen-silicon bond in M-ESiMe3 and the
complexes serving as a soluble source of “metallachalcogenolate”, ME–. Using Nheterocyclic carbenes (NHC) as ancillary ligands in this class of complex, we set out
to increase the thermal stability of M-ESiMe3with improved control of reactivity
during ternary MM´E cluster formation. The preparation of a series of NHC ligated
copper-chalcogenolate complexes of the general formula [(IPr)Cu-ESiMe3] (IPr = 1,3bis(2,6-diisopropylphenyl)imidazolin-2-ylidene; E = S, Se, Te) will be described.
These are prepared selectively in high yield with demonstrated utility as precursors
for ternary MM´E. The reaction of [(IPr)Cu-SSiMe3] with mercuric(II) acetate affords
the complex [{(IPr)CuS}2Hg] (1) containing two (IPr)Cu-S- fragments bonded to a
central Hg(II) (see Figure 1).[1] The synthesis of the isostructural silver complexes,
[(IPr)Ag-ESiMe3] (E = S, Se) and their reactivity toward metal salts will be also
presented. Using the smaller NHC ligand 1,3-di-isopropylbenzimidazole-2-ylidene
(iPr2-bimy), the preparation of such stable Cu-ESiMe3 (E = S, Se) is also possible, and
X-ray analysis illustrates that these exist as the dimers [(iPr2-bimy)2Cu2(μ-ESiMe3)2]
in the solid state. The reactivity of these molecules for the formation of ternary
clusters will be described and compared to that of [(IPr)Cu-ESiMe3].
Figure 1. Molecular Structure of 1.
References:
[1] M. Azizpoor Fard, F. Weigend, J. F. Corrigan, Chem. Commun, 2015, DOI: 10.1039/c5cc00940e.
Oral presentation - C03
Reactivity and Structure-Building Principles of LiCKOR Base
Mixtures in THF
Ulrike Kroesen, Stephan G. Koller, Kathrin Louven and Carsten Strohmann*
mail@carsten-strohmann.de
Faculty of Chemistry and Chemical Biology, TU Dortmund University
Otto-Hahn-Str. 6, Ger-44227, Dortmund
The iC OR superbase or “Schlosser’s base” constitutes an important component in
the tool kit of organometallic chemists.[1] It is comprised of a mix of an alkyllithium
reagent, usually n-butyllithium (“ iC”), and a bulky alkoxide of a heavier alkaline
metal, typically potassium tert-butoxide (“ OR”). Their metalating power exceeds
that of their single components by far. This synthetically well exploited synergic
increase in reactivity has recently attracted our interest as the successful structural
elucidation of species arising from LiCKOR mixtures, especially in the commonly
used polar solvent THF, remains a challenge.[2] Herein, we present the structures of
the species formed from reaction mixtures containing LiCKOR components and
substrates which undergo metalation by this base mix even at –78 °C in THF.
Furthermore, the synthetic value of a Schlosser’s base-mediated metalation under
mild conditions was demonstrated using dimethylphenethylamine.[3] This
pharmaceutically attractive synthetic building block can be selectively metalated in
the benzylic position by LiCKOR mixtures at low temperatures. Thus, decomposition
of the ß-metalated intermediate via elimination is efficiently avoided and its
conversion with electrophiles can be achieved.
Acknowledgements: We are grateful to the Deutsche Forschungsgemeinschaft (DFG) and the Fonds
der Chemischen Industrie (FCI) for financial support
References:
[1] a) M. Schlosser, Angew. Chem. Int. Ed. 2005, 44, 376–393; b) L. Lochmann, Eur. J. Inorg. Chem.
2000, 1115–1126; c) M. Schlosser, Pure Appl. Chem. 1988, 60, 1627–1634.
[2] a) S. Harder; A. Streitwieser, Angew. Chem. Int. Ed. Engl. 1993, 1066–1068; b) A. R. Kennedy; J.
G. MacLellan; R. E. Mulvey, Angew. Chem. Int. Ed. 2001, 40, 3345–3347.
[3] a) C. Unkelbach; H. S. Rosenbaum; C. Strohmann, Chem. Commun. 2012, 48, 10612–10614; b) C.
Unkelbach, D. F. O'Shea, C. Strohmann, Angew. Chem. Int. Ed. 2014, 53, 553–556.
Oral presentation - C04
Functional metal-organic molecules and materials derived from rigid
and flexible P-N scaffolds
Ramamoorthy Boomishankar*
boomi@iiserpune.ac.in
Department of Chemistry, Indian Institute of Science Education and Research
(IISER), Pune
Dr. Homi Bhabha Road, Pune - 411008, India
Employing phosphoramide ligands of formula, (RNH)3PO in reaction with Pd(OAc)2,
a facile route to access the highly basic trianions, [(RN)3PO]3‒ ((X)3‒) analogous to
PO43− ion was developed. The (X)3‒ ligand, containing a central binding group, acts as
a rigid cis-blocking ligand and stabilizes trimeric or prismatic Pd(II) cluster of
formula {Pd3X(OAc)3}1or2.[1] Further, the trinuclear (Pd3X)3+ motifs have been
utilized as supramolecular synthons for obtaining neutral cluster cages for Pd(II) ions
in tetrahedral and cubic topologies via a bridging ligand substitution strategy.[2] In
contrast, phosphoramides containing peripheral metal binding groups provide a
flexible ligand platform and yield multi-metallic assemblies in various dynamic
architectures.[3] By using 3-pyridyl functionalized dipodal phosphoramide ligand (L)
we were able to generate interesting examples of Cu IIL2 frameworks that show anion
dependent structure and ferroelectric behaviour.[4]
Figure 1. (a) Formation of a neutral tetrahedral cage, and its selective guest uptake behaviour;
(b) Anion driven Cu(II) assemblies and their structure dependent physical properties.
Acknowledgements: This work was supported by IISER, Pune and the SERB, DST, India through
Grant No. SR/S1/IC-50/2012.
References:
[1] A. K. Gupta, S. A. D. Reddy and R. Boomishankar, Inorg. Chem. 2013, 52, 7608.
[2] A. K. Gupta, A. Yadav, A. K. Srivastava, K. R. Ramya, H. Paithankar, S. Nandi, J. Chugh and R.
Boomishankar, Inorg. Chem. 2015, 54, DOI: 10.1021/ic502798r.
[3] (a) A. K. Gupta, S. S. Nagarkar and R. Boomishankar Dalton Trans. 2013, 42, 10964; (b) A. K.
Gupta, A. K. Srivastava, I. K. Mahawar and R. Boomishankar Cryst. Growth Des. 2014, 14, 1701.
[4] A. K. Srivastava, B. Praveen Kumar, I. K. Mahawar, P. Divya, S. Shalini and R. Boomishankar
Chem. Mater. 2014, 26, 3811.
Oral presentation - C05
Chlorine/oxygen transfer reactions of [PCl2N]3 using oxygenated
Lewis bases as a possible route to [PON]3
Benjamin S. Thome, Savannah R. Snyder, Joanna M. Beres, Patrick O. Wagers,
Matthew J. Panzner, Brain D. Wright, Wiley J. Youngs, Claire A. Tessier*
tessier@uakron.edu
Department of Chemistry, University of Akron
190 E Buchtel Commons, Akron, OH, 44325-3601, USA
The reactions of [PCl2N]3 with a variety of oxygen containing Lewis bases (O=E =
HMPA, OPEt3 and DMF) result in Cl/O exchange. The reactions occur via a two-step
process (Fig. 1) which involves
1) formation of an intermediate salt [P3N3Cl5O] [E-Cl]+ and
2) attack by O=E to form P3N3Cl4O-O=E and [E-Cl]+[Cl]-.
In addition to spectral characterizations, both phosphazene products of the HMPA
reactions have been characterized by X-ray crystallography. As shown by reaction
chemistry and the Gutmann-Beckett Lewis acidity scale, the P=O of the phosphazene
ring in P3N3Cl4O-O=E has a strong Lewis acid character. We are investigating the use
of more vigorous reaction conditions, other O=E and metal catalysis to promote the
types of reactions in Fig. 1 on all the P atoms of the phosphazene ring with the goal of
preparing [PON]3 or its base-stabilized adducts. Such molecules could be precursors
to novel PNO materials
Acknowledgements: We thank ICL and OMNOVA Foundation for support of this work.
Oral presentation - C06
Phosphorus heterocycles from Na(OCP)
Zoltán Benkő, Dominikus Heift, Hansjörg Grützmacher
zbenko@mail.bme.hu
Department of Inorganic and Analytical Chemistry, Budapest University of
Technology and Economics
Szent Gellért tér 4. H-1111, Budapest
Sodium phosphaethynolate, Na(OCP), has been shown to be a simple and easily
accessible one-phosphorus building block for transition metal complexes and
heterocycles, furthermore, it can also undergo nucleophilic reactions and
cycloadditions. As it will be presented, Na(OCP) reacts with two equivalents of
dicyclohexylcarbodiimide (DCC) to yield an anionic, imino-functionalized 1,3,5diazaphosphinane, shown on the left in the figure below. The oxidation of this anion
with elemental iodine causes an intramolecular rearrangement reaction to give a
bicyclic 1,3,2-diazaphospholenium cation (depicted on the right). The “Umpolung” of
the electronic properties from non-aromatic to highly aromatic is reversible and the
cation is reduced with elemental magnesium to give back the 1,3,5diazaphosphinanide anion. High level theoretical calculations on the reaction
mechanisms suggest that phosphinidene species are involved in the rearrangement
processes.[1]
Figure 1. The chemically reversible redox triggered interconversion of the monocyclic anion
and the bicyclic cation
References:
[1] D. Heift, Z. Benkő, H. Grützmacher, Angew. Chem. Int. Ed., 2014, 53, 6757-6761
Oral presentation - C07
Terpene Main Group Chiral Derivatives: Catalytic Activity in
Polymerization and C-H Activation Processes
Marta E. G. Mosquera,* María Fernández-Millán, Ghaita Chahboun, Jesús Cano,
Tomás Cuenca
martaeg.mosquera@uah.es
Department of Organic Chemistry and Inorganic Chemistry
Alcalá University, Campus Universitario, 28805-Alcala de Henares, Madrid. Spain
Chiral catalysts have provided very efficient systems that allow the preparation of
enantiomerically pure derivatives. Interestingly, the number of well-defined main
group complexes described with chiral ligands is remarkably lower than the transition
metal counterparts, even though main group coordination compounds are active in a
variety of important catalytic processes.[1] In this context, one of our ongoing research
areas is focused on the preparation of homo and heterometallic aluminium complexes
with O- and N- donor ligands and the study of their activity in catalytic
polymerization processes.[2] We have extended these studies to O- and N- donor chiral
ligands using naturally occurring compounds. In particular, we used terpenoids since
they are excellent ligand precursors.[3] From them it is possible to prepare
multifunctional pro-ligands, by adding an extra functional group such as an alcohol or
an oxime moiety. These multifunctional molecules can furnish polymetallic chiral
coordination compounds by the reaction with the appropriate metallic precursors.
These studies have led us to prepare new chiral derivatives with unusual structures,
which are active in catalytic ROP polymerization processes and also in the activation
of C-H bonds in carbonyl compounds.
Figure 1. Terpene based aluminium heterometallic chiral compound
References:
[1] The Renaissance of Main group Chemistry; Themed Issue, Dalton Transactions, 2008, 4321.
[2] (a) G. Martínez, J. Chirinos, M. E. G. Mosquera, T. Cuenca, E. Gómez, Eur. J. Inorg. Chem, 2010,
1522; (b) V. Tabernero, M. E. G. Mosquera, T. Cuenca, Organometallics, 2010, 29, 3642; (c) G.
Martínez, M. E. G. Mosquera, T. Cuenca, Eur. J. Inorg. Chem, 2012, 3611; (d) García-Valle, F. M.;
Estivill, R.; Gallegos, C.; Cuenca, T.; Mosquera, M. E. G.; Tabernero, V.; Cano, J. Organometallics
2015, 34, 477.
[3] M. S. Ibn El Alami, M. A. El Amrani, F. Agbossou-Niedercorn, I. Suisse, A. Mortreux, Chem. Eur.
J. 2015, 21, 1398.
Oral presentation - C08
Reactions of Aryl and Hetaryl Thioketones with Pt(0) Complexes;
Ferrocenyl Substituted Platinathiiranes
Grzegorz Mlostoń (a), Sebastian Gröber (b), Wolfgang Weigand (b)
gmloston@uni.lodz.pl
a) Department of Organic & Applied Chemistry, University of Łódź,
PL-91-403 Łódź, Tamka 12, Poland
b) Institute of Inorganic & Analytical Chemistry, University of Jena,
D-07743 Jena, Humboldtstr. 8, Germany
In a series of recent publications, reactions of 1,2,4-trithiolanes with L2Pt(0)
complexes (L2= bisphosphane), leading to the formation of platinathiiranes 1, side by
side with dithiolato complexes 2, were reported.[1] On the other side, heterocycles 1
can be prepared in high yields by treatment of aromatic and cycloaliphatic thioketones
with Pt(0)-phosphine complexes in toluene solution.[2] In our ongoing studies on the
chemistry of thiocarbonyl compounds, a series of new aryl/hetaryl thioketones,
including representatives bearing ferrocenyl moiety, was prepared and successfully
applied as novel building blocks for the synthesis of sulfur heterocycles with variable
ring size. In the communication, reactions of aryl/hetaryl thioketones 3 with L2Pt(0)
complexes, leading to new derivatives of platinathiiranes 1 will be presented.
Molecular structures of isolated products were established by means of spectroscopic
methods, and in some cases confirmed by using the X-ray crystallography.
Acknowledgements: The authors thank the National Science Center (Cracow, Poland) for financial
support within the grant Maestro (Grant Maestro-3 (Dec-2012/06/A/ST5/00219)
References:
[1] a) T. Weisheit, A. Kriltz, H. Görls, G. Mloston, W. Imhof, W. Weigand, Chem. Asian J. 2012, 7,
1383; b) H. Petzold, S. Brätigam, H. Görls, W. Weigand, M. Celeda, G. Mloston, Chem. Eur. J. 2006,
12, 8090.
[2] W. Weigand, R. Wünsch, C. Robl, G. Mloston, H. Nöth, M. Schmidt, Z. Naturforsch. 2000, 55b,
453.
Oral presentation - C09
Poster
Presentations
Photocyclization of Dimesitylborylarenes
Naoki Ando, Tomokatsu Kushida, Aiko Fukazawa, Shuhei Iyoyama, Yoshihito
Shiota, Kazunari Yoshizawa, and Shigehiro Yamaguchi
andou.naoki@c.mbox.nagoya-u.ac.jp
Graduate School of Science, Nagoya University, Institute for Materials Chemistry and
Engineering, Kyushu University, Institute of Transformative Bio-Molecules, Nagoya
University
Furo, Chikusa, Nagoya 464-8602, Japan 744 Motooka, Nishi-ku, Fukuoka 819-0395,
Japan
The isosterism of tri-coordinated boron and carbocation imparts intriguing reactivity
and properties to boron-containing π-conjugated systems. We have recently reported a
new mode of photoreaction for tri-coordinate organoboron compounds, which is the
bora-Nazarov cyclization of a 9-dimesitylboryl-substituted dibenzoborepin.[1] In the
course of study on the substrate scope of the bora-Nazarov cyclization, we found that
dimesitylboryl-substituted thiophene underwent a new mode of photoreaction to
produce a spirocyclic boraindane in good yield. To gain insight into this reaction,
theoretical calculations were conducted, which suggest that this new photoreaction
proceed through a [1,6] sigmatropic H-rearrangement to form a biradical intermediate,
followed by the intramolecular radical coupling to afford the spirocyclic product. The
study on the substrate scope showed that this reaction has generality and a series of
dimesitylboryl-substituted arenes undergo this photoreaction exclusively instead of
the bora-Nazarov cyclization.
References:
[1] A. Iida, S. Saito, T. Sasamori, S. Yamaguchi, Angew. Chem. Int. Ed. 2013, 52, 3760.
Poster presentation - P001
Chelating bis(diazaboryl) ligands for preparation of cyclic bisboryl
complexes
Eugene L. Kolychev, Rémi Tirfoin, Simon Aldridge*
evgeny.kolychev@chem.ox.ac.uk
Inorganic Chemistry Department, University of Oxford
Chemistry Research Laboratory, Mansfield road 12, OX1 3TA, Oxford
Recent reports by Yamashita and Nozaki et al. on the isolation[1] and reactivity[2] of
the first stable boryllithium reagent have opened new possibilities for the application
of diazaboryl fragments as strong σ-donor anionic ligands. Preliminary studies
conducted in our laboratory showed that diazaboryl complexes of Main Group
elements[3] are encouraging candidates as transition metal free bond activation
reagents. Further investigation is currently focused on the preparation of bifunctional
boryl ligands, with the aims (i) of increasing the stability of complexes by the chelate
effect, and (ii) of facilitating re-reduction to lower oxidation states due to the presence
of constrained ring systems with appropriately narrow bite angles. Synthetically, key
precursors for such chelate systems are bis(diazaboryl) dibromides which can be
prepared by high yielding procedures starting from commercially available starting
materials. In subsequent steps, a range of approaches including metathesis using alkali
metal boryl complexes and oxidative insertion of low valent metal centres into B-H
bonds of the analogous boryl hydrides have been examined to establish reliable
synthetic routes to chelating boryl complexes.
Figure 1. Cyclic bis(diazaboryl) complexes.
Acknowledgements: ELK gratefully acknowledges financial support by the FP7-Marie Curie IEF
grant 626441.
References:
[1] Y. Segawa, M. Yamashita, K. Nozaki, Science, 2006, 314, 113.
[2] Y. Segawa, Y. Suzuki, M. Yamashita, K. Nozaki, J. Am. Chem. Soc., 2008, 130, 16069.
[3] (a) A.V. Protchenko, K. Hassomal Birjkumar, D. Dange, A.D. Schwarz, D. Vidovic, C. Jones, N.
Kaltsoyannis, P. Mountford, S. Aldridge, J. Am. Chem. Soc., 2012, 134, 6500. (b) A.V. Protchenko, D.
Dange, A.D. Schwarz, M.P. Blake, C. Jones, P. Mountford, S. Aldridge, J. Am. Chem. Soc., 2014, 136,
10902. (c) A.V. Protchenko, M.P. Blake, A.D. Schwarz, C. Jones, P. Mountford, S. Aldridge,
Organometallics, 2015, in press, DOI:10.1021/om501252m
Poster presentation - P002
Synthetic Applications of Borylzinc Compounds: Boryl Transfer
Chemistry and Catalytic Borylation.
Jesús Campos, Simon Aldridge*
jesus.camposmanzano@chem.ox.ac.uk
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford,
South Parks Road, Oxford OX1 3QR, United Kingdom
Since the groundbreaking isolation of the first boryllithium species by Yamashita and
Nozaki,[1] the chemistry of boryl nucleophiles has rapidly expanded. Interestingly, the
reactivity of the boryl anion is highly dependent on its metallic counterion. For
instance, the behaviour of a diaminosubstituted boryllithium and its magnesium
analogue when added to benzaldehyde is highly dissimilar,[2] with the former leading
to borylbenzylalcohol and the latter to benzoylborane. Considering the rich chemistry
of alkyl zinc reagents in synthetic applications and the growing interest in zinc as an
inexpensive and environmentally benign metal in catalysis, we decided to explore the
still undeveloped chemistry of borylzinc compounds (A in Figure 1). [Figure 1]
Transmetalation reactions using borylzinc species allowed us to synthesize a number
of Transition Metal and Main Group metal boryl complexes with considerably higher
yields and increased selectivity when compared to the commonly used boryllithium
analogues. More interestingly, the direct use of borylzinc precursors for crosscoupling processes resulted in the borylation of a plethora of organic halides and
pseudohalides, including unactivated alkyl halides, in high yields, with high
functional group tolerance and under mild conditions.
Figure 1. Synthetic applications of borylzinc compounds
Acknowledgements: JC thanks Agencia Andaluza del Conocimiento (Spain) and European
Commission for a Talentia Postdoc/Marie Curie Fellowship.
References:
[1] Y. Segawa, M. Yamashita, K. Nozaki, Science, 2006, 314, 113.
[2] M. Yamashita, Y. Suzuki, Y. Segawa, K. Nozaki, J. Am. Chem. Soc. 2007, 129, 9570.
Poster presentation - P003
Well-Defined Boralumoxanes as Convenient MAO Modelling
Compounds
Harmen S. Zijlstra, Sjoerd Harder*
harmen.zijlstra@fau.de
Deparment of Pharmacy and Chemistry, University of Erlangen-Nürnberg
Egerlandstrasse 1, 91058 Erlangen
Ever Since its serendipitous discovery methylalumoxane (MAO) has grown from an
academic curiosity to an industrial commodity. Despite its importance as an activator
in homogeneous polymerization catalysis its exact structure and working mechanism
remain debated.1 Isolobal exchange of a "MeAlO2" unit in MAO for a "RBO2" moiety
can lead to defined model compounds that still maintain their activating capabilities.
Such a boralumoxane has been obtained by Hessen et al.2 Upon reaction of tBu3Al
with a boronic acid (DIPP)B(OH)2 a well-defined tetrameric cluster was obtained
(Scheme 1). The obtained complex could be fully characterized and was shown to be
able to activate simple ziroconene precatalysts.3 Using the same principle we have
expanded the scope of boronic acids used and synthesized several new, well-defined
complexes. Depending on the boronic acid substituent and the B:Al ratio used a
variety of different boralumoxanes can be obtained. These clusters are capable of
activating simple ziroconocene precatalysts in various ways that depend on their
structure. Due their structural variety and activating capabilities these boralumoxanes
provide insight into the structure and possible activation mechanisms of MAO.
Scheme 1. Synthesis of a well-defined boralumoxane (Ar= 2,6-di-iPr-Phenyl; DIPP)
Acknowledgements: This research forms part of the reserach program of the Dutch Polymer Institute
(DPI), projects #310 and #728
References:
1) H. S. Zijlstra, S. Harder, Eur. J. Inorg. Chem. 2015, 1, 19-43.
2) B. Richter, A. Meetsma, B. Hessen, J. H. Teuben, Chem. Comm. 2001, 14, 1286-1287.
3) B. Richter, A. Meetsma, B. Hessen, J. H. Teuben, Angew. Chem. Int. Ed. 2002, 41, 2166-2169.
Poster presentation - P004
Syntheses, structural characterization and DFT investigations of
pentaborate salts templated by substituted pyrrolidinium cations
Charlotte L. Jones,(a) Michael A. Beckett,(a) R. Andrew Davies,(a) Peter N.
Horton(b)
charlotte.jones@bangor.ac.uk
School of Chemistry
(a) Bangor University, Bangor, Gwynedd, LL57 2UW, UK; (b) University of
Southampton, Southampton, SO17 1BJ, UK
Non-metal pentaborate derived materials could be seen as alternatives to B2O3 for
hydrogen storage; B2O3has been proposed as a potential hydrogen store[1] which
meets the US Department of Energy's requirements of being capable of storing 6%
wt. H2. A series of pentaborate salts have been synthesized, containing substituted
pyrrolidinium cations. Characterizations were carried out using spectroscopic and Xray diffraction methods. Thermal properties were determined using TGA;
condensation of the pentaborate network occurs between 200-300°C, before formation
of B2O3 at 600°C. All compounds show extensive supramolecular H-bonded anionic
lattices. H-bond interactions and motifs found in these and in other pentaborate
structures have been examined and modelled by DFT calculations, confirming that Hbonds interactions in pentaborates are moderately strong (ca. −10 to −21 kJ mol−1)
and are likely to dominate the energetics of their templated syntheses[2].
Figure 1. Diagrams of the (a) pyrrolidinium cations and (b) the pentaborate1− anion, as found
within the synthesized salts.
References:
[1] S.H. Jhi, Y.K. Kwon, K. Bradley, J.C.P. Gabriel, Solid State Commun., 2004, 129, 769-773.
[2] M.A. Beckett, S.J. Coles, R.A. Davies, P.N. Horton, C.L. Jones, Dalton Trans., 2015, 44, in press,
published online 10th March 2015, DOI: 10.1039/c5dt00248f.
Poster presentation - P005
Study of reactivity of germylene stabilized by boraguanidinate ligand
Jiří Böserle , ibor Dostál
jiri.boserle@student.upce.cz
Department of General and Inorganic Chemistry, University of Pardubice
Studentská 573, CZ-53210, Pardubice
The investigation dealing with reactivity of germylene 1 (Fig. 1) containing in its
structure a boraguanidinate ligand is presented. This type of dianionic N,N’-chelating
ligands is derived from guanidinate ligands by a substitution a carbon atom by a boron
atom and represents a relatively unexplored branch of organometallic chemistry[1].The
electronic and steric properties of these ligands may be fine-tuned by the use of
different substituents on the BN3 backbone[2]. Another interesting property of these
ligands is dianionic character which significantly affects their reactivity[2]. Herein, we
report on the synthesis of the rare example of boraguanidinate-stabilized germylene 1
and its reactivity with selected reagents. Observed results show that 1 may be a
promising candidate for activation of various compounds especially small molecules.
Figure 1. Structure of studied germylene 1.
Acknowledgements: The authors thank the Grant agency of the Czech Republic project no.
P207/12/0223.
References:
[1] Ch. Fedorchuk, M. Copsey, T. Chivers, Coord. Chem. Rev., 2007, 251, 897-924.
[2] A. M. Corrente, T. Chivers, Inorg. Chem., 2008, 47, 10073-10080.
Poster presentation - P006
Reactions of a Barrelene-type Dialumane Bearing Bulky Aryl
Substituents with Lewis Bases
Koichi Nagata, Tomohiro Agou, Takahiro Sasamori, Norihiro Tokitoh*
nagata_k@boc.kuicr.kyoto-u.ac.jp
Institute for Chemical Research, Kyoto University
Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011,
Japan
Recently, we have reported the synthesis of dialumane 1 bearing barrelene-like
scaffold and its dialumene-unit transfer reactions (Tbb–Al=Al–Tbb) from 1 to other
arenes (naphthalene and anthracene) via [2+4] cycloaddition reaction between the
dialumene and the arenes.[1] Herein, we will describe the reactions of 1 with Lewis
bases, in the expectation of trapping the corresponding the dialumene. Reaction of 1
with N,N-dimethyl-4-aminopyridine (DMAP) afforded the Lewis acid-base adduct 2.
In contrast the treatment of 1 with 2 equivalents of tert-butyl isocyanide gave ring
expansion product 3, via the insertion of one molecule of tert-butyl isocyanide to the
Al–Al bond of 1 (Scheme 1).[2] Structures and properties of the newly obtained ring
system containing two Al atoms, 2 and 3 will be discussed.
Scheme 1. Reactions of barrelene-type dialumane 1 with Lewis bases.
References:
[1] T. Agou, K. Nagata, N. Tokitoh, Angew. Chem. Int. Ed. 2013, 52, 10818.
[2] Example of insertion reactions of isocyanides to Al–Al single bond: (a) W. Uhl, U. Schütz, Z.
Anorg. Allg. Chem. 1995, 621, 823. (b) W. Uhl, U. Schütz, S. Phol, W. Saak, Z. Anorg. Allg. Chem.
1996, 622, 373. (c) W. Uhl, U. Schütz, W. Hiller, M. Heckel, Chem. Ber. 1994, 127, 1587.
Poster presentation - P007
In-Situ Activation of C-C Multiple Bonds Mediated by AmidinatoAluminium Framework
Tomáš Chlupatý , Michal Bílek, Zdeňka Růžičková, Aleš Růžička
tomas.chlupaty@upce.cz
Department of General and Inorganic Chemistry, Faculty of Chemical Technology
University of Pardubice, Studentská 573, CZ-532 10, Pardubice, Czech Republic
The activation of electron-rich fragments, such as multiple bonds, by low-valent main
group metal complexes and their subsequent chemical transformations represent one
of the most-important fields in modern organic and organometallic chemistry. Modern
utilizations of these complexes, however, present numerous challenges both to the
electronic and steric properties of stabilizing ligands that are currently investigated.
Versatile bonding modes, high electron density and potential steric shielding of
amidinato ligands predetermine their main group metal complexes to be excellent
candidates for these studies[1] (especially economic and environmental friendly
aluminium from the point of view of modern chemistry). The synthesis, structure and
reactivity of amidinato-aluminium complexes, which could be utilized as promoters
of in-situ activation of usaturated C-C systems, will be discussed in this paper. Some
reactivity of target diphenylethylene-bridged dinuclear aluminium amidinates toward
small molecules will be also demonstrated.
Figure 1. Synthesis and reactivity of diphenylethylene-bridged dinuclear aluminium
amidinate.
Acknowledgements: Authors would like to thank the Grant Agency of Czech Republic (grant nr.
P207/12/0223) for financial support.
References:
[1] for example: (a) S. J. Bonyhady, D. Collis, G. Frenking, N. Holzmann, C. Jones, A. Stasch, Nature
Chem., 2010, 2, 865-869; (b) L. Fohlmeister, S. Liu, C. Schulten, B. Moubaraki, A. Stasch, J. D.
Cashion, K. S. Murray, L. Gagliardi, C. Jones, Angew. Chem. Int. Ed., 2012, 51, 8294-8298; (c) K.
Junold, J. A. Baus, C. Burschka, R. Tacke, Angew. Chem. Int. Ed., 2012, 51, 7020–7023; (d) Y. Li, K.
C. Mondal, J. Lubben, H. Zhu, B. Dittrich, I. Purushothaman, P. Parameswaran, H. W. Roesky, Chem.
Commun., 2014, 50, 2986-2989.
Poster presentation - P008
New aluminate compounds of low nuclearity: synthesis and catalytic
activity studies.
M.T. Muñoz, Tomás Cuenca, Marta E.G. Mosquera*
teresa.munoz@edu.uah.es
Departamento de Química Orgánica y Química Inorgánica, University of Alcalá
Ctra. Madrid-Barcelona Km. 33,600, E-28805, Alcalá de Henares (Madrid)
Aluminium is a fascinating metal due to its exciting structural chemistry and
remarkable activity in catalysis.[1] In particular, aluminium alkoxide or aryloxide
species have shown to be very active catalysts in ROP processes of epoxides or cyclic
esters.[2] In addition, aluminium heterometallic compounds are very interesting
species, especially when the metals are connected by an oxygen atom, since those
compounds have shown to be very active catalysts in polymerization reactions. [3] In
this context, our research is centred in the preparation of new aluminium homo and
heterometallic compounds active in polymerization processes.We have synthesized
new aryloxide derivatives bearing functionalized aryl moieties, in those the presence
of the additional functional group in the aromatic ring offered extra coordination
points that provide them with new structural features.[4] The extension of those studies
to highly bulky phenols has allowed us to prepare heterometallic derivatives with
unusual low nuclearity (figure 1).
Figure 1. New heterobimetallic aluminium-sodium compound.
References:
[1] (a) A. C. Gledhill, N. E. Cosgrove, T. D. Nixon, C. A. Kilner, J. Fisher, T. P. Kee, Dalton Trans.,
2010, 39, 9472; (b) M. Brasse, J. Cámpora, M. Davies, E. Teuma, P. Palma, E. Álvarez, E. Sanz, M. L.
Reyes, Adv. Synth. Catal., 2007, 349, 2111.
[2] (a) G. Martínez, S. Pedrosa, V. Tabernero, M. E. G. Mosquera, T. Cuenca, Organometallics, 2008,
27, 2300; (b) H. Sugimoto, C. Kawamura, M. Kuroki, T. Aida, S. Inoue, Macromolecules, 1994, 27,
2013.
[3] (a) Y. Ning, H. Zhu, E. Y. X. Chen, J. Organomet. Chem. 2007, 692, 4535; (b) A. RodriguezDelgado, E. Y. X. Chen, J. Am. Chem. Soc. 2005, 127, 961.
[4] (a) M. T. Muñoz, C. Urbaneja, M. Temprado, M. E. G. Mosquera, T. Cuenca, Chem. Commun.
2011, 47, 11757; (b) M. T. Muñoz, T. Cuenca, M. E. G. Mosquera, Dalton Trans. 2014, 43, 14377.
Poster presentation - P009
Aminotroponate ligand stabilized pentacoordinate aluminium (III)
complexes: Synthesis and structural characterization
Mahendra Kumar Sharma, Soumen Sinhababu, and Selvarajan Nagendran*
msiitdilli@gmail.com
Department of Chemistry, Indian Institute of Technology Delhi
Hauz Khas, New Delhi 110 016, India
Through the reaction of lithium salt of 2-ibutylamino tropone [(2-ibu)AT] with AlCl3
(0.5 equiv.) in toluene stable pentacoordinate aluminium monochloride [(2i
bu)AT]2AlCl 1 has been isolated in good yield as yellow solid. The reaction of
compound 1 with 1 equiv. of PhLi, 2-thienyllithium and AgOTf afforded [(2i
bu)AT]2AlPh 2, [(2-ibu)AT]2AlSC4H3 3 and [(2-ibu)AT]2AlOTf 4 complexes,
respectively. Further, Compound 4 was reacted with 1 equiv. of
dimethylaminopyridine
gave
pentacoordinate
cationic
complex
[(2i
i
bu)AT]2Al(DMAP)(OTf) 5. A similar reaction of 2- butylamino tropone with AlMe3
(0.5 equiv.) in toluene afforded [(2-ibu)AT]2AlMe 6. Further, Compound 6 was
treated with H2O (0.5 equiv.) gave, alumoxane complex {[(2-ibu)AT]2Al}2O 7 as a
yellow solid. All the novel pentacoordinate aluminium compounds 1-7 have been
characterized through multi-nuclear NMR spectroscopy. Further, were characterized
through single crystal X-ray diffraction studies.
Figure 1. Molecular structure of pentacoordinate alumoxane complex 7.
References:
[1] (a) Asay, M.; Jones, C.; Driess, M. Chem. Rev. 2011, 111, 354. (b) Nagendran, S.; Roesky, H. W.
Organometallics 2008, 27, 457.
[2] Cui, C.; Roesky, H. W.; Schmidt, H.-G.; Noltemeyer, M.; Hao, H.; Cimpoesu, F. Angew. Chem.
Int. Ed. 2000, 39, 4272.
[3] Bakthavachalam, K.; Reddy, D. N. Organometallics 2013, 32, 3174.
Poster presentation - P010
“Strained” Metal Bonding Environments in Indium(III) Dithiolates
and Their Use as Lewis Acid Catalysts
Timothy S. Anderson (a), Glen G. Briand (a)*, Andreas Decken (b), Courtney M.
Dickie (a), Thomas I. Kostelnik (a), Heidi M. Pickard (a) and Michael P. Shaver (c)
gbriand@mta.ca
(a) Department of Chemistry and Biochemistry, Mount Allison University, Sackville,
Canada
(b) Department of Chemistry, University of New Brunswick, Fredericton, Canada
(c) School of Chemistry, University of Edinburgh, Edinburgh, UK
There has been increasing interest in main group metals as alternatives to expensive
and toxic transition and rare earth metals as catalysts for chemical transformations.[1]
Notably, indium reagents are well-established Lewis acid catalysts in organic
syntheses, though the majority of compounds that have been studied include simple
trivalent salts such as triflates, chlorides and oxides.[2] More recently, organometallic
indium alkoxide and amide compounds have been shown to be useful for the ring
opening polymerization (ROP) of cyclic esters to yield biodegradable polymers.[3] We
are interested in developing the potentially rich and “tunable” reaction chemistry of
Lewis acidic main group organometallic complexes. Indium thiolates are attractive
candidates for such studies due to the favorability of the In-S bond, which allows for
the facile synthesis and hydrolytic stability of target compounds. Further, polydentate
oxo- and amino-dithiolate ligands with appropriately chosen architectures may
provide “strained” indium bonding environments (e.g. 1 vs 2) and reactive species.
Our recent studies into the synthesis and structural characterization of 1) methyl
indium dithiolates and their use as Lewis acid cataylsts for the ring opening
polymerization (ROP) of cyclic esters [4] and 2) cationic indium dithiolate complexes
and their suitability as water tolerant Lewis acid catalysts for organic reactions in
aqueous media will be presented.
References:
[1] (a) S. Kobayashi, M. Ueno, T. Kitanosono, Top. Curr. Chem. 2012, 311, 1; (b) T. Chivers, J. Konu,
Comm. Inorg. Chem. 2009, 30, 131.
[2] U. Schneider, S. Kobayashi, Acc. Chem. Res. 2012, 45, 1331.
[3] S. Dagorne, M. Normand, E. Kirillov, J.F. Carpentier, Coord. Chem. Rev. 2013, 257, 1869.
[4] L.E.N. Allan, G.G. Briand, A. Decken, J.D. Marks, M.P. Shaver and R.G. Wareham. J. Organomet.
Chem., 2013,736, 55.
Poster presentation - P011
Aluminacycles Derived from the Imidazolin-2-iminato Ligand
Daniel Franz, Shigeyoshi Inoue*
daniel.franz@tu-berlin.de
Institut für Chemie, Technische Universität Berlin
Straße des 17. Juni 135, GER-10623, Berlin
The imidazolin-2-iminato ligand possesses pronounced 2σ- and 2π- or π electrondonating character and steric fine-tuning is easily accomplished.[1] We exploit these
properties for the syntheses of main group metal hydrides with applications in the
field of bond activation.[2] The dimeric aluminum dihydride 1 reacts with yellow
sulfur or selenide metal to afford the aluminum hydrogensulfide 2a[2b] or
hydrogenselenide 2b (Figure). The tellurium compound 3 is formed upon conversion
of 1 with Bu3P=Te and is marked by an Al2N2 ring decorated by a ditelluride unit. The
formation of 3 contrasts the reactivity of 1 with lower chalcogenides. The remaining
hydrides at the aluminum atoms in 2 and 3 allow for further functionalization at the
metal centers: Hitherto unknown types of aluminum halide hydrogenchalcogenide
complexes (4) are accessible via conversion of 2 with N-bromosuccinimide (NBS) or
N-iodosuccinimide (NIS).
Figure 1. Syntheses of hydrogenchalcogenides 2 and 4, as well as the ditelluride 3; a: E = S,
b: E = Se, X = Br or I, Dip = 2,6-diisopropylphenyl.
References:
[1] X. Wu, M. Tamm, Coord. Chem. Rev. 2014, 260, 116.
[2] (a) D. Franz, E. Irran, S. Inoue, Dalton Trans. 2014, 43, 4451; (b) D. Franz, S. Inoue, Chem. Eur. J.
2014, 20, 10645; (c) D. Franz, S. Inoue, Chem. Asian. J. 2014, 9, 2083; (d) D. Franz, E. Irran, S. Inoue,
Angew. Chem. Int. Ed. 2014, 53, 14264.
Poster presentation - P012
NHC-stabilized Silylphosphinoalanes / -gallanes
Manuel Kapitein, Carsten von Hänisch
kapitein@students.uni-marburg.de
Fachbereich Chemie, Philipps-Universität Marburg
Hans-Meerwein-Straße 4, 35043 Marburg
Since compounds containing elements of groups 13 and 15 have been in the focus of
research, they appear mainly in form of (poly)cyclic structures. Therein, stabilization
of this compounds is achieved through intramolecular Lewis acid-base bonds between
the group 15 lone pair and the group 13 metal.[1,2] Herein we present new examples of
this structural type, which contain bulky substituents on both, metal and phosphorus
atoms. With the tBu2-functionality at the metal atom as well as the tBuPh2Si-group,
the steric hindrance is nearly maximized. For many of this cyclic compounds we were
able to cleave the ring with the help of N-heterocyclic carbenes and obtain monomeric
NHC:M(R2)-P(H)SiR3species, which are unknown until recently (Fig.1a).[3] Besides
this, structures of cyclic aluminum / gallium-phosphorus four membered rings with
Lewis base stabilized metal atoms as well as free phosphorus lone pairs are displayed
(Fig.1b).[4]
Figure 1. Schematic pathway to monomeric species and molecular structure of an example (a)
and a Lewis acid stabilized cycle and the corresponding HOMO (b).
References:
[1] R. L. Wells, Coord. Chem. Rev. 1992, 112, 273–291.
[2] M. Matar, S. Schulz, U. Flörke, Zeitschrift für Anorg. und Allg. Chemie 2007, 633, 162–165.
[3] M. Kapitein, C. von Hänisch, Eur. J. Inorg. Chem. 2015, 2015, 837–844.
[4] M. Driess, S. Kuntz, K. Merz, H. Pritzkow, Chem. Eur. J. 1998, 4, 1628–1632.
Poster presentation - P013
Reactivity of N→Ga Coordinated Organogallium compounds
T. Řičica, R. Jambor, Z. Růžičková
st26877@student.upce.cz
Department of general and inorganic chemistry
University of Pardubice, Faculty of Chemical Technology, Studentská 95, 53210
Pardubice, Czech Republic
The N→Ga coordinated organogallium dichlorides L1-3GaCl2[1] (1 - 3) containing
either N,C,N-chelating ligands L1-2 (L1 is 2,6-(Me2NCH2)2C6H3- and L2 is {(2,6iPr2C6H3)N=CH}2C6H3-) or C,N-chelating ligand L3 (L3 = {(2-iPr2C6H3)N=CH}-4,6tBu2C6H2-) were prepared (Chart 1). The substitution reactions of 1 – 3 with Li2X (X
= S, Se, Te), KC8, or LiNEt2 were further studied. The products of those reactions will
be discussed.
Acknowledgements: The authors would like to thank the Grant Agency of the Czech Republic (1507091S and 15-07912S) for financial support.
References:
[1] Yamaguchi., Science of Synthesis., 2004, 7, 387.
Poster presentation - P014
Synthesis of Gallium Chalcogenide Clusters with Organic
Functionality
Katharina Hanau, Stefanie Dehnen*
Hanau@students.uni-marburg.de
Department of Chemistry, Philipps-Universität Marburg
Hans-Meerwein-Str. 4, DE-35032 Marburg
The synthesis of organo-functionalized germanium and tin chalcogenide clusters has
been well-established over the last few years. Depending on the used elements and the
organic moiety, different structural motives were obtained, and both the inorganic
clusters and the organic moieties had been modified in different reactions, which
resulted in compound with interesting properties.[1,2] Replacing the group 14 elements
with group 13 elements, such as gallium, the formation of new compounds with
different properties can be expected. For this purpose, the hydrogallation of alkynes
with HGaCl2[3] is a necessary first step to link functional groups to the gallium atom.
The alkenyl chloro gallanes that are obtained this way can then be reacted with
chalcogenide sources to generate organo-functionalized gallium chalcogenide
clusters, the structural motives of which are to be determined by single crystal x-ray
diffraction analysis.
Figure 1. Synthesis of alkenyl chloro gallanes and subsequent experiment.
References:
[1] (a) Z. Hassanzadeh Fard, C. Müller, T. Harmening, R. Pöttgen, S. Dehnen, Angew. Chem. 2009,
121, 4507 – 4511. (b) S. Heimann, M. Holynska, S. Dehnen, Z. Anorg. Allg. Chem. 2012, 638, 1663 –
1666. (c) J. P. Eußner, B. E. K. Barth, E. Leusmann, Z. You, N. Rinn, S. Dehnen, Chem. Eur. J. 2013,
19, 13792 – 13802.
[2] (a) Z. Hassanzadeh Fard, L. Xiong, C. Müller, M. Holynska, S. Dehnen, Chem. Eur. J. 2009, 15,
6595 – 6604. (b) Z. Hassanzadeh Fard, R. Clérac, S. Dehnen, Chem. Eur. J. 2010, 16, 2050 – 2053.
[3] W. Uhl, M. Claesener, Inorg. Chem. 2008, 47, 4463 – 4470.
Poster presentation - P015
Hume-Rothery Phase-inspired molecular chemistry – Synthesis of
intermetalloid transition metal/group 13 clusters
Jana Weßing, Chelladurai Ganesamoorthy, Christian Gemel, Roland A. Fischer*
jana.wessing@rub.de
Chair of Inorganic Chemistry II, Ruhr-University Bochum
Universitätsstr. 150, 44801 Bochum, Germany
In light of the growing significance of nanoalloys in material science, the
investigation of their molecular congeners, that is closely-related mixed-metal
clusters, has aroused interest as a means to elucidate properties of the respective
parent materials. In this regard, the synthesis of Hume-Rothery Phase-derived clusters
combining transition metals (TM) and group 13 elements (E) is particularly
challenging. In this contribution, we will present a novel pathway towards
intermetalloid TM/E clusters based on the coordination chemistry of the exotic ligand
ECp* (Cp* = pentamethylcyclopentadienyl) at TM centers. The reaction of AlCp*
with [(IPr)AuH] or [PPh3CuH]6 yields [Au8(AlCp*)6] and [Cu6(AlCp*)6H4],
respectively, the first representatives of this new class of homoleptic ECp*-decorated
TM clusters.[1] Even larger clusters are accessible, as proven by the synthesis of
[Cu43(AlCp*)12] from [Cu6(AlCp*)6H4] and [Cu(Mes)]5 (Mes = mesityl). All these
systems feature mixed-metal cores comprising nested polyhedra of “naked“ TM
centers and ligated Al atoms, which, for [Cu6(AlCp*)6H4], are related to structural
motifs of well-known Hume-Rothery Phases, such as Cu5Zn8. Additionally,
[Cu6(AlCp*)6H4] reacts with benzonitrile in a hydrometallation reaction to give
[Cu6(AlCp*)6(N=CHPh)H3], which may serve as a molecular equivalent of potential
intermediates in hydrogenation reactions at Hume-Rothery nanophases, as reported by
Armbrüster et al.
Figure 1. Molecular structures of [Cu6(AlCp*)6H4], [Cu43(AlCp*)12] and [Au8(AlCp*)6].
References:
[1] C. Ganesamoorthy, J. Weßing, C. Kroll, R.W. Seidel, C. Gemel, R.A. Fischer, Angew. Chem. Int.
Ed. 2014, 53, 7943.
Poster presentation - P016
The impact of silyl-groups in β-position on the electronic systems of
phospholes
Andreas Kirchmeier, Dieter Klintuch, Rudolf Pietschnig*
andreas.kirchmeier@uni-kassel.de
Chemische Hybridmaterialien, Institut für Chemie, Universität Kassel
Heinrich-Plett-Straße 40, 34132, Kassel, Germany
In the last decades the chemistry and properties of phospholes have been investigated
thoroughly.[1] Because of the conjugation and tunability of their π-systems they were
found to be very attractive building blocks as organic semiconductors.[2] Although a
lot of phosphole derivatives were synthesized by changing the functional groups at the
phosphorus atom or in α-position, the effect on the opto-electronic characteristics of
substituents in β-position only recently started to emerge.[3] Therefore we present a
general and flexible synthetic method for introducing functional groups in β-position
of phospholes. According to our procedure we synthesized phospholes with silylgroups in the backbone (see figure 1) and investigated the resulting optical properties.
Figure 1. Structural motif of the synthesized phospholes.
References:
[1] (a) F. Mathey, Chem. Rev., 1988, 88, 429-453. (b) F. Mathey, Coord. Chem. Rev., 1994, 137, 1-52.
[2] (a) T. Baumgartner, R. Réau, Chem. Rev., 2006, 106, 4681-4727. (b) M. Hissler, P. W. Dyer, R.
Réau, Coord. Chem. Rev., 2003, 244, 1-44.
[3] O. Fadhel, Z. Benkö, M. Gras, V. Deborde, D. Joly, C. Lescop, L. Nyulászi, M. Hissler, R. Réau,
Chem. Eur. J., 2010, 16, 11340-11356.
Poster presentation - P017
n and π Complexes of NHC-stabilized Disilicon(0)
Marius I. Arz, Gregor Schnakenburg, Alexander C. Filippou*
m.arz@uni-bonn.de
Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn
Gerhard-Domagk-Straße 1, GER-53121, Bonn
Various silicon species in low oxidation states are important intermediates in
chemical vapour deposition for the production of semiconductors and solar cells or in
the Müller-Rochow process. Recent developments in molecular silicon chemistry
revealed that N-heterocyclic carbenes (NHCs) are capable of stabilizing silicon
centers in unusual low oxidation states. Intriguing examples are the Si(II)-halides
SiX2(NHC) (X = Cl, Br, I; NHC = N-heterocyclic carbene) and SiClAr(NHC), which
have been shown to be versatile building blocks in low-valent silicon chemistry.[1] In
comparison, the reactivity of the zerovalent silicon compounds (NHC)Si=Si(NHC)
(1)[2a] and Si(bNHC) (b(NHC) = bis(N-heterocyclic carbene))[2b] still needs to be
explored. Recently, we reported on the isolobal relationship of compound 1, the
phosphasilenylidene ArP=Si(NHC) and diphosphenes ArP=PAr (Ar = aryl group),
bearing similar frontier orbitals with an almost isoenergetic n+ (E–E) lone pair orbital
(HOMO) and π(E–E) orbital (HOMO−1).[3] Herein, we report our studies on the
complexation reactions of 1 with coinage d10 metal centers (M = CuI,[4] AgI, AuI), in
which both n (η1) and π (η2) coordination modes are observed.
Figure 1. Acyclic (η1) and cyclic (η2) coordination modes of compound 1.
References:
[1] See for example: a) A. C. Filippou, O. Chernov, K. W. Stumpf, G. Schnakenburg, Angew. Chem.
Int. Ed. 2010, 49, 6700; b) A. C. Filippou, B. Baars, O. Chernov, Y. N. Lebedev, G. Schnakenburg,
Angew. Chem. Int. Ed. 2014, 53, 565; c) Y. N. Lebedev, U. Das, O. Chernov, G. Schnakenburg, A. C.
Filippou, Chem. Eur. J. 2014, 20, 9280.
[2] a) Y. Wang, Y. Xie, P. Wei, R. B. King, H. F. Schaefer III, P. v. R. Schleyer, G. H. Robinson,
Science 2008, 321, 1069; b) Y. Xiong, S. Yao, S. Inoue, J. D. Epping, M. Driess, Angew. Chem. Int.
Ed. 2013, 52, 7147.
[3] D. Geiß, M. I. Arz, M. Straßmann, G. Schnakenburg, A. C. Filippou, Angew. Chem. Int. Ed. 2015,
54, 2739.
[4] See also: M. Chen, Y. Wang, Y. Xie, P. Wei, R. J. Gillard, Jr., N. A. Schwartz, H. F. Schaefer III,
P. v. R. Schleyer, G. H. Robinson, Chem. Eur. J. 2014, 20, 9208.
Poster presentation - P018
A H-substituted Silylium Ion
Henning Großekappenberg, Katherina Rüger, Dennis Lutters and Thomas Müller*
henning.grossekappenberg@uni-oldenburg.de
Carl von Ossietzky University Oldenburg Institute of Chemistry
Carl von Ossietzky Straße 9-11, 26129 Oldenburg, Federal Republic of Germany
In the recent past a series of intramolecular stabilized silylium ions were synthesized
and well investigated.[1] Intriguingly [Si-H]-substituted silylium ions have not been
observed in condensed phase yet.[2] Here we present the ambitious synthesis of these
highly reactive compounds (Figure).[3] The challenge is to find the right balance
between sterically demanding substituents, which are necessary for kinetic
stabilization, while keeping the hydride accessiblefor Bartlett–Condon–Schneider
(BCS) hydride transfer reaction. Proton coupled 29Si INEPT NMR experiment is an
easy way to identify the [Si‑H] functionality of such compounds (Figure).
Figure 1. Synthesis by BCS hydride transfer reaction and proton coupled silicon INEPT NMR
of silylium ion 2.
References:
[1] (a) S. Duttwyler, Q.-Q. Do, A. Linden, K. K. Baldridge, J. S. Siegel, Angew. Chem. 2008, 120,
1743-1746; (b) T. Müller, in Functional Molecular Silicon Compounds I, Vol. 155 (Ed.: D.
Scheschkewitz), Springer International Publishing, 2014, pp. 107-162.
[2] (a) I. S. Ignat’ev, T. A. Kochina, D. V. Vrazhnov, Russ. J. Gen. Chem. 2007, 77, 575-580; (b) G.
Rasul, J. L. Chen, G. K. S. Prakash, G. A. Olah, J. Phys. Chem. A 2010, 114, 4394-4399; (c) D. G.
Gusev, O. V. Ozerov, Chemistry – A European Journal 2011, 17, 634-640; (d) A. F. DeBlase, M. T.
Scerba, T. Lectka, M. A. Johnson, Chem. Phys. Lett. 2013, 568–569, 9-13.
[3] C. Gerdes, W. Saak, D. Haase, T. Müller, J. Am. Chem. Soc. 2013, 135, 10353-10361.
Poster presentation - P019
Activation of 7-Silanorbornadienes by NHCs – A Fast and Selective
Way to NHC Stabilized Hydridosilylenes
Dennis Lutters, Thomas Müller*
dennis.lutters@uni-oldenburg.de
Institute of Chemistry, Carl von Ossietzky Universität Oldenburg
Carl von Ossietzky Straße 9-11, 26129 Oldenburg, Federal Republic of Germany
7-Silanorbornadienes such as 1[1,2] are known to be a source of silylenes by
thermolysis and photolysis.[3] A new method for the preparation of hydridosilylenes
such as 3 is the activation of 7-silanorbornadienes 1 with N-heterocyclic carbenes e.g.
2. In a fast and selective reaction at room temperature NHC stabilized hydridosilylene
3 can be synthesized via the elimination of anthracene from 1. Up to now only a few
examples of such species are known.[4,5] The reactivity of compound 3 towards
acetylenes and metal complexes will be presented.
Figure 1. Activation of 7-silanorbornadiene 1 by NHC 2 to hydridosilylene 3.
References:
[1] T. Sasamori, S. Ozaki, N. Tokitoh, Chem. Lett. 2007, 36, 588.
[2] C. Gerdes, W. Saak, D. Haase, T. Müller, J. Am. Chem. Soc. 2013, 135, 10353.
[3] For a recent summary, see M. Okimoto, A. Kawachi, Y. Yamamoto, J. Organomet. Chem. 2009,
694, 1419.
[4] R. Rodriguez, D. Gau, Y. Contie, T. Kato, N. Saffon-Merceron, A. Baceiredo, Angew. Chem. Int.
Ed. 2011, 50, 11492.
[5] S. Inoue, C. Eisenhut, J. Am. Chem. Soc. 2013, 135, 18315.
Poster presentation - P021
Synthesis and Reactivity of an NHC-stabilized Silicon(I) Dimer
Yuk-Chi Chan and Cheuk-Wai So*
CWSo@ntu.edu.sg
Division of Chemistry and Biological Chemistry, School of Physical and
Mathematical Sciences
Nanyang Technological University, 637371 Singapore
The chemistry of novel base-stabilized heavier group 14 element(I) dimers [LË-ËL]
(E = Si, Ge, Sn and Pb; L = amidinate, guanidinate, β-diketiminate, N-functionalized
aryl, P-functionalized amide, etc) has attracted much attention in the past ten years.[1]
They comprise a Ë-Ë single bond and a lone pair of electrons on each E atom. Their
structures resemble the singly bonded structure of the heavier alkyne analogues of
composition LEEL.Their reactivities showed that they are powerful reagents for the
activation of small molecules, unsaturated substrates etc. Recently, several research
groups demonstrated that a variety of reactive moieties can be isolated with the aid of
N-heterocyclic carbene.[2] As such, we are interested in investigating whether an Nheterocyclic carbene is capable of stabilizing group 14 element(I) dimers. In this
poster, we report the synthesis of the NHC-stabilized silicon(I) dimer 2 and its
reactions with various substrates will be presented.
Scheme 1. Synthesis of NHC-stabilized silicon(I) dimer 2.
Acknowledgements: This work was supported by ASTAR SERC PSF grant.
References:
[1] Selected articles : a) S.-P. Chia, R. Ganguly, Y. Li, C.-W. So, Organometallics 2012, 31, 64156419; b) S.-P. Chia, H.-X. Yeong, C.-W. So, Inorg. Chem. 2012, 51, 1002-1010; c) S.-P. Chia, H.-W.
Xi, Y. Li, K. H. Lim, C.-W. So, Angew. Chem., Int. Ed. 2013, 52, 6298-6301.
[2] Selected articles : a) Y. Wang, Y. Xie, P. Wei, R. B. King, H. F. Schaefer III, P. v. R. Schleyer and
G. H. Robinson, Science, 2008, 321, 1069–1071; b) R. S. Ghadwal, H. W. Roesky, S. Merkel, J. Henn
and D. Stalke, Angew. Chem., Int. Ed., 2009, 48, 5683–5686; c) A. C. Filippou, O. Chernov, B. Blom,
K. W. Stumpf and G. Schnakenburg, Chem.–Eur.J., 2010, 16, 2866–2872.
Poster presentation - P022
The Silyldisilene-Cyclotrisilane Equilibrium
Isabell Omlora, Max Holthausenb, Josef Wenderb, and David Scheschkewitza*
i.omlor@mx.uni-saarland.de
(a) Krupp-Chair of General and Inorganic Chemistry, Saarland University,
Am Markt, Zeile 1, GER-66125, Saarbrücken-Dudweiler
(b) Institute of Inorganic and Analytical Chemistry,
Max-von-Laue-Str. 7, GER-60438 Frankfurt am Main
Already in the first report on a stable cyclotrisilane (Mes6Si3; Mes = 1,3,5
trimethylphenyl) Masamune et al. disclosed the photolytic generation of disilenes
from such ring systems.[1] This prompted intense investigations into synthesis and
reactivity of such compounds.[2] One possible approach based on the silyldisilene 1 cyclotrisilane 2 equilibrium (Scheme 1) had been discussed theoretically early on [3],
but realized experimentally only recently.[4] Treatment of a disilenide
(Tip2Si=Si(Tip)Li; Tip=2,4,6-triisopropylphenyl) with an excess of chlorosilane
provides access to various functionalized cyclotrisilanes. In the present contribution
solid state structures of donor-acceptor complexes of possible intermediates of the
silyldisilene-cyclotrisilane equilibrium will be presented.
Scheme 1: The silyldisilene 1 - cyclotrisilane 2 equilibrium.
References:
[1] S. Masamune, Y. Hanzawa, S. Murakami, T. Bally, J. F. Blount, J. Am. Soc., 1982, 104, 4, 1150.
[2] M. Weidenbruch, Chem. Rev., 1995,95, 1479.
[3] A. Sax, Chem. Phys. Lett., 1986, 129,1, 66.
[4](a) D. Scheschkewitz, K. Abersfelder, J. Am. Chem. Soc., 2008, 130, 4114; (b) D. Scheschkewitz, K.
Abersfelder, A. J. P. White, H. S. Rzepa, Science,2010, 327, 564.
Poster presentation - P023
Reactivity of cyclotrisilene with multiply-bonded molecules
Hui Zhao, Michael J. Cowley, Moumita Majumdar, Volker Huch, David
Scheschkewitz*
s8huzhao@stud.uni-saarland.de
Krupp-Chair of General and Inorganic Chemistry, Saarland University
66125 Saarbrücken-Dudweiler, Germany
The cyclotrisilene motif as the heavier cousin of cyclopropene is particular inasmuch
as that its bonding situation and hence reactivity can be expected to be governed by
the considerable ring strain imposed by the three-membered ring.[1] Research reveal
the cyclotrisilene shows reactivity towards less reactive unsaturated compounds. For
instance, synthesis of functionalized cyclic disilenes via ring expansion of
cyclotrisilenes with isocyanides was reported by Sekiguchi and Scheschkewitz.[2] In
addition, carbonylation of cyclotrisilenes be achieved by employing CO.[3] Very
recently, the phosphide delivery to a cyclotrisilene was also disclosed.[4] Here we
report the reactivity of cyclotrisilene with molecules with carbon-carbon triple bond
as well as nitrogen-nitrogen double bond. All of the reactions proceed under mild
conditions. Cyclotrisilene 1 react with diphenylacetylene and 1,4-bis(ethynyl)benzene
produce the 1:1 adducts 2 and 3, alternatively. In the case of azobenzene, the double
bond of two nitrogen atoms is cleaved, resulting in a five-membered ring with a weak
interaction between the two Si atoms which connected with two N atoms.
Figure 1. Reactions of cyclotrisilene with diphenylacetylene and 1,4-bis(ethynyl)benzene
(above) and with azobenzene (below).
References:
[1] Wu, W., B. Ma, J. I-Chia Wu et al. Chem. Eur. J. , 2009, 15, 9730-9736.
[2] Ohmori, Y., M. Ichinohe, A. Sekiguchi et al. Organometallics, 2013, 32, 1591-1594.
[3] Cowley, M. J., Y. Ohmori, V. Huch et al. Angew. Chem. Int. Ed., 2013, 52, 13247-13250.
[4] Robinson, T. P., Cowley, M. J, D. Scheschkewitz et al. Angew. Chem. Int. Ed., 2014, 54, 683-686.
Poster presentation - P024
Metal-Silicon Triple Bonds: [2+2] Cycloadditions of Alkynes and
Heteroalkynes
Bernhard Baars, Oleg Chernov, Gregor Schnakenburg, Alexander C. Filippou*
bbaars@uni-bonn.de
Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn
Gerhard-Domagk-Straße 1, GER-53121 Bonn
Metallacyclobutadienes are key intermediates in the metathesis of alkynes, which has
become an important tool in organic synthesis. Studies on heavier group 14 element
homologues of this important class of organometallic compounds are very rare. First
metallasilacyclobutadienes have been obtained recently upon [2+2] cycloaddition of
alkynes across the metal-silicon triple bonds of molybdenum[1] and osmium[2]
silylidyne complexes. Here we report on the reactions of unprecedented cationic
group 6 metal silylidyne complexes[3] (1) with alkynes and heteroalkynes, and the full
characterization of the resulting metallasilacyclobutadienes displaying diverse
bonding modes.
Acknowledgements: We thank the Deutsche Forschungsgemeinschaft (SFB 813) for the generous
financial support of this work.
References:
[1] O. Chernov, Novel molecular Si(II) precursors for synthesis of the first compounds with metalsilicon triple bonds (Ph.D. thesis), University of Bonn, 2012 http://hss.ulb.unibonn.de/2012/2994/2994.html.
[2] a) P. G. Hayes, Z. Xu, C. Beddie, J. M. Keith, M. B. Hall, T. D. Tilley, J. Am. Chem. Soc. 2013,
135, 11780; b) Z. Xu, M. B. Hall, Inorg. Chim. Acta 2014, 422, 40.
[3] A. C. Filippou, B. Baars, O. Chernov, Y. N. Lebedev, G. Schnakenburg, Angew. Chem. 2014, 126,
576; Angew. Chem. Int. Ed. 2014, 53, 565.
Poster presentation - P025
Consecutive Synthesis of Novel Cage-like Bicyclic Trisiloxanes
Dominik Keiper, Michael Feierabend, Carsten von Hänisch*
Keiper@students.uni-marburg.de
Department of Chemistry, Philipps-Universität Marburg
Hans-Meerwein-Straße 4, GER-35032, Marburg
The bicyclic trisiloxanes we discuss on the poster are cagelike compounds, including
two eight-membered ring systems. Both bridgehead atoms are connected via three
O(SiMe2)2-units. These substances are considered as inorganic analogues of cryptands
and also of [3.3.3]bicycloundecane, the so-called manxane.[1] Until now, some
derivatives consisting of different bridgehead atoms and possible substituents are
known.[2] However, there has been only one compound including silicon at this
position so far.[3] Now we report the synthesis of novel bicyclic trisiloxanes of this
kind with different functional groups at the bridgehead silicon atoms. The hydrolysis
and condensation of the branched tetrasilane PhSi(SiMe2Cl)3 (1) with hydrochloric
acid yielded the bicyclic trisiloxane Ph-Si{O(SiMe2)2}3Si-Ph (2). After
protodephenylation of 2 with trifluoromethanesulfonic acid CF3SO3H (TfOH) the
triflyl-substituted compound 3 was obtained. Our current work focusses on the
halogenation of 3 by reaction with various halides AX (Figure 1).[4]
Figure 1. Consecutive synthesis of novel bicyclic trisiloxanes.
References:
[1] M. Doyle et al., Tetrahedron Lett., 1970, 42, 3619-3622.
[2] (a) C. Eaborn, P. B. Hitchcock, P. D. Lickiss, J. Organomet. Chem., 1983, 252, 281-288; (b) C. von
Hänisch, F. Weigend, O. Hampe, S. Stahl, Chem. Eur. J., 2009, 15, 9642-9646; (c) C. Bimbös, M. Jost,
C. von Hänisch, K. Harms, Eur. J. Inorg. Chem., 2013, 4645-4653.
[3] S. S. Al-Juaid, Y. Derouiche, P. B. Hitchcock, P. D. Lickiss, J. Organomet. Chem., 1988, 341, 241245.
[4] (a) M. Feierabend, PhD thesis, Marburg, 2013; (b) D. Keiper, master's thesis, Marburg, 2014; (c)
M. Feierabend, D. Keiper, C. von Hänisch, manuscript in preparation.
Poster presentation - P026
Metal─Silicon Multiple Bonds: Metallasilylidynes and
Metallasilacumulenes
Priyabrata Ghana, Gregor Schnakenburg, Alexander C. Filippou*
pghana@uni-bonn.de
Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn
Gerhard-Domagk-Strasse 1, GER-53121 Bonn
Complexes containing a multiply bonded carbon atom embedded between two
transition metal centers are known since the 1980’s. Two types of these complexes
have been described, the metallacumulenes (LnM=C=MLn)[1] and the metallacarbynes
(L n M≡C─M n).[2] In comparison, studies on related silicon complexes have not been
reported so far. This can be traced back to two intrinsic properties of silicon, which
are its reluctance to form double and even more triple bonds and its anomalous low
electronegativity. These properties render the isolation of metallasilacumulenes and
metallasilylidynes a very challenging goal. In the present work a systematic approach
to these unprecedented classes of compounds is reported taking advantage of the
specific stereoelectronic properties of scorpionato ligands. The target complexes 1
and 2 have been analyzed by quantum theory, and first reactions will be reported.
Acknowledgements: We thank the Deutsche Forschungsgemeinschaft (SFB 813) for the generous
financial support of this work.
References:
[1] V. L. Goedken, M. R. Deakin, L. A. Bottomley, J. Chem. Soc. Chem. Commun. 1982, 607.
[2] S. L. Latesky, J. P. Selegue, J. Am. Chem. Soc. 1987, 109, 4731.
Poster presentation - P027
The Versatile Reactivity of an NHC-stabilized Silicon(II)
Monohydride
Carsten Eisenhut, Tibor Szilvási, Shigeyoshi Inoue*
carsten.eisenhut@mailbox.tu-berlin.de
Department of Chemistry, Technische Universität Berlin
Straße des 17. Juni 115, GER-10623, Berlin
Since the first isolation of an N‑heterocyclic silylene, a number of silylenes have been
isolated by taking advantage of thermodynamic and kinetic stabilization. However,
the chemistry of silylene hydrides is hardly explored due to their highly reactive
nature. Silylene hydrides are of great interest because of their potential for diverse
applications and can generally be isolated by utilizing a donor (Lewis base) and an
acceptor (Lewis acid) stabilization. In this contribution, we report on the synthesis and
reactivity of the novel acceptor-free silylene hydride 1 equipped with an Nheterocyclic carbene (NHC) as supporting ligand (Figure 1).[1] Interestingly, this
NHC-stabilized silylene hydride 1 features three reactive sites (the lone pair on
silicon, the Si-H bond, and the NHC). In fact, silylene 1 shows versatile reactivities
towards transition metal complexes and unsaturated organic compounds. For
example, the silylene-iron complex 2 was isolated from the reaction of 1 with
Fe2(CO)9, whereas silylene 1 reacts with Ni(COD)2 to afford the dihydrodisilene
complex 3. Moreover, the reactions of 1 with acetylenes afforded silole 4 via [2+2+1]
cycloaddition and 1-alkenyl-1-alkynylsilane 5 via the C-H abstraction depending on
the substrate.[2] In addition, DFT calculations suggest that NHC-supported
zwitterionic transition states and intermediates play a significant role in these reaction.
Figure 1. Selected reactivities of the silylene monohydride 1.
References:
[1] S. Inoue, C. Eisenhut, J. Am. Chem. Soc. 2013, 135, 18315.
[2] C. Eisenhut, T. Szilvasi, N. C. Breit, S. Inoue, Chem. Eur. J. 2015, 21, 1949.
Poster presentation - P028
SYNTHESIS OF INTRAMOLECULARLY COORDINATED
ORGANOSILANES
M. Novák, R. Jambor
miroslav.novak@student.upce.cz
Department of General and Inorganic Chemistry, Faculty of Chemical Technology,
University of Pardubice
Studentská 573, Pardubice 532 10, Czech Republic
Organosilanes play important roles in many areas of organic syntheses. Hydrosilanes
R3Si–H are useful reagents for the hydrosilylation of multiple bonds, reduction of
various functional groups, preparation of a silanols R3Si–OH, etc.1 Our attempts to
synthesize an N→Si intramolecularly coordinated organosilanes of general formula
PhL1,2SiHR (where L1 and L2 are C,N-chelating ligands containing CH=N imine
group and R is Ph or H) yielded organosilicon amides possessing silaindole structural
motive in their structures (see Figure 1).2 Isolated organosilicon amides are an
outcome of the spontaneous hydrosilylation of the CH=N imine moiety induced by
N→Si intramolecularly coordination. This unexpected fact initiated us to extend the
spontaneous hydrosilylation induced by N→Si intramolecularly coordination also to
N,N-chelating ligands derived from pyridine or 1H-pyrrol and for that study we
efficiently used trichlorosilane as hydrosilylation agent.
Acknowledgements: The authors would like to thank the Grant Agency of the Czech Republic (1507091S) for financial support.
References:
1 a) M. A. Brook, Silicon in Organic, Organometallic, and Polymer Chemistry, Wiley, 2000, ch. 8, p.
171–188; b) P. D. Lickiss, Adv. Inorg. Chem.1995, 42, 147.
2 M. Novák, . Dostál, M. Alonso, F. De Proft, A. Růžička and R. Jambor, Chem. Eur. J., 2014, 20(9),
2542.
Poster presentation - P029
A Highly Reactive “Half-Parent” Phosphasilene and Iminosilane
LSi=EH (E = N, P)
Kerstin Hansen, Tibor Szilvási, Burgert Blom and Matthias Driess
kerstin.hansen@tu-berlin.de
Technische Universität Berlin, Department of Chemistry
Strasse des 17. Juni 135, GER-10623 Berlin, Germany
Double bond species with silicon and elements of the 15th group have attracted
considerable attention owing to their high reactivity, which is induced by the
pronounced polarity of the Siδ+-Eδ- (E = N, P) bond.[1] Herein we report the synthesis
of a highly ylidic phosphasilene and iminosilane with a PH and NH moiety,
respectively.[2-4] Both compounds are labile in solution and show different reactivities.
The reaction of DMAP with the „half-parent“ phosphasilene affords the donorstabilized form, whereas the reaction with the iminosilane resulted in the activation of
the α C-H bond of DMAP. To further elucidate the experimentally observed
reactivity, DFT calculations were carried out and will be presented.
Figure 1. Above: “Half-Parent” Phosphasilene Below: “Half-Parent” Iminosilane.
References:
[1] R. C. Fischer, P. P.Power, Chem. Rev. 2010, 110, 3877.
[2] K. Hansen, T. Szilvási, B. Blom, S. Inoue, J.-D. Epping, M. Driess, J. Am. Chem. Soc. 2013, 135,
11795.
[3] K. Hansen, T. Szilvási, B. Blom, E. Irran, M. Driess, Chem. Eur. J. 2014, 20, 1947.
[4] K. Hansen, T. Szilvási, B. Blom, M. Driess, J. Am. Chem. Soc. 2014, 136, 14207.
Poster presentation - P030
Reactivity of Phosphorus-functionalized Low-valent Silicon
Compounds towards Transition Metal Complexes
Nora C. Breit, Shigeyoshi Inoue
nora.breit@tu-berlin.de
Department of Chemistry, Technische Universität Berlin
Straße des 17. Juni 135, GER-10623 Berlin
Low-valent silicon compounds have high potentials for applications in catalysis,
organic synthesis, and materials science. Silylenes with an electron lone pair on
silicon and silenes marked by an element-silicon double bond are the key players in
this field. The incorporation of phosphorus into these species induces polarized bonds
based on their different electronegativities and gives rise to novel properties and
reactivities. In spite of their intriguing prospect, the reactivity of phosphinosilylenes
and phosphasilenes with transition metals is scarcely studied. We focus on the
reactivity of phosphinosilylene 1 and phosphasilene 2 (Figure 1).[1] 1 and 2 are
additionally featuring trimethylsilyl (TMS) groups that can shift from phosphorus to
silicon and back or be completely removed.[1,2] Hence, novel pathways as observed in
reactions of 2 with group 10 transition metals affording 3 and 4 are available.[3] In this
presentation we give a short overview on the reactions previously described for 1 and
2 and subsequently focus on our newest results. In reactions of 1 and 2 with tungsten
and iron carbonyl complexes species 5 and 6 were obtained that are suitable for in
depth studies.[4]
Figure 1. Reactivity of phosphinosilylene 1 and phosphasilene 2 towards nickel, platinum,
iron, and tungsten complexes.
References:
[1] S. Inoue, W. Wang, C. Präsang, M. Asay, E. Irran, M. Driess, J. Am. Chem. Soc. 2011, 133, 2868.
[2] N. C. Breit, T. Szilvási, S. Inoue, Chem. Eur. J. 2014, 20, 9312.
[3] N. C. Breit, T. Szilvási, T. Suzuki, D. Gallego, S. Inoue, J. Am. Chem. Soc. 2013, 135, 17958.
[4] N. C. Breit, T. Szilvási, S. Inoue, manuscript under preparation.
Poster presentation - P031
A Low Valent Silicon-Rhodium and -Cobalt Four-Membered Ring
Sabrina Khoo, Cheuk-Wai So*
ykhoo004@e.ntu.edu.sg
Division of Chemistry and Biological Chemistry, School of Physical and
Mathematical Sciences
Nanyang Technological University Singapore 637371
Base-stabilized heavier group 14 element(I) dimers of composition [LË-ËL] (E = Si,
Ge, Sn and Pb; L = supporting ligand) have attracted much attention in the past few
years due to their unique structures and reactivities.[1] They are stabilized kinetically
by a variety of ligands such as amidinate, guanidinate, β-diketiminate, Nfunctionalized aryl and P-functionalized amide etc. They are powerful reagents, which
resemble transition metal complexes to activate small molecules and unsaturated
substrates. However, their reactivity toward transition metal complexes are underdeveloped. In this poster, we report the reaction of the amidinate-stabilized silicon(I)
dimer [L1SiSiL1] (1; L1 = PhC(NtBu)2) with [Rh(cod)Cl]2 and CoBr2 to form
complexes comprising Si2M2 rings (M = Rh, Co), respectively. They were
characterized by NMR spectroscopy, X-ray crystallography and DFT calculations.
Figure 1. Synthesis of the Si2Rh2 ring 2.
Acknowledgements: This work is supported by AcRF Tier 1 grant
References:
[1] Selected articles : a) S.-P. Chia, R. Ganguly, Y. Li, C.-W. So, Organometallics 2012, 31, 64156419; b) S.-P. Chia, H.-X. Yeong, C.-W. So, Inorg. Chem. 2012, 51, 1002-1010; c) S.-P. Chia, H.-W.
Xi, Y. Li, K. H. Lim, C.-W. So, Angew. Chem., Int. Ed. 2013, 52, 6298-6301.
Poster presentation - P032
Synthesis and Properties of Silicon Based Crown Ether Analogues
Kirsten Reuter, Carsten von Hänisch*
kirsten.reuter@staff.uni-marburg.de
Department of Chemistry, Philipps-Universität Marburg
Hans-Meerwein Straße 4, GER-35043, Marburg
Cyclosiloxanes are compared to organic crown ethers less attractive for the
complexation of cations. This is due to the low basicity of oxygen in siloxanes and to
date different explanations are discussed.[1] Intriguingly, recent studies have shown
that the basicity of oxygen is increased at the presence of Si2-units, for example in the
cylic silaether (Me4Si2O)2.[2] Our research is focused on disilane based crown ether
analogues and their complexation potential. At the first step, one ethane unit of a
crown ether has formally been substituted by disilane. Study of the alkaline metal
complexes confirms the increased coordination potential of disilane based crown
ethers: The bond length of silicon substituted oxygen to the metal is slightly shortened
compared to the organic substituted oxygen atoms.
Figure 1. Hybrid crown ethers with one disilane unit.
Acknowledgements: We thank the Deutsche Forschungsgemeinschaft for financial support
References:
[1] S. Grabowsky, M. F. Hesse, C. Paulmann, P. Luger, J. Beckmann, Inorg. Chem. 2009, 48, 4384.
[2] M. Cypryk, J. Kurjata, J. Chojnowski, J. Organomet. Chem. 2003, 686, 373
Poster presentation - P033
Configurationally Stable Pentaorganosilicates
Leon J. P. van der Boon, J. Chris Slootweg, Koop Lammertsma and Andreas W.
Ehlers*
l.j.p.vander.boon@vu.nl
Department of Chemistry and Pharmaceutical Sciences, VU University Amsterdam
de Boelelaan 1083, 1081 HV, Amsterdam, the Netherlands
Silicon is capable of forming hypercoordinate structures with more than four
substituents. Usually, these structures are only found as reactive intermediates, but
they can be stabilized by withdrawing electron density from the silicon centre. Most
of these hypercoordinate silicon species contain nitrogen or oxygen as they bind
strongly to silicon. However, it is also possible to obtain pentaorganosilicates with
five carbon substituents using stabilizing bisaryl ligands (Figure 1, top).[1]
Pentaorganosilicates, like most pentacoordinate species, show dynamic behavior via
multiple Berry pseudorotations (Figure 1, bottom) and therefore any chiral
information is lost due to permutations of the substituents.[2] We now present a full
experimental and theoretical study on pentaorganosilicates 1 and 2 with substituents
that inhibit the vital Berry pseudorotation making these silicates configurationally
stable, thereby retaining chiral information. These concepts are also viable for
pentacoordinate metal complexes, were inhibition of the Berry pseudorotation is key
for a successful application in asymmetric catalysis. Therefore, coupling of
catalytically active metals via the pyridine moiety in silicate 3 is also investigated.
Figure 1. Top: Various pentaorganosilicates, bottom: The Berry pseudorotation.
Acknowledgements: This work was supported by the Council for Chemical Sciences of the
Netherlands Organization for Scientific Research (NWO/CW).
References:
[1] E.P.A. Couzijn, J.C. Slootweg, A.W. Ehlers, K. Lammertsma, Z. Anorg. Allg. Chem., 2009, 635,
1273.
[2] E.P.A. Couzijn, J.C. Slootweg, A.W. Ehlers, K. Lammertsma, J. Am. Chem.. Soc., 2009, 131, 3741.
Poster presentation - P034
Functionalization and Transfer of Unsaturated Si6 Cluster
Compounds
Philipp Willmes, Kai Abersfelder, Volker Huch, David Scheschkewitz*
p.willmes@mx.uni-saarland.de
Krupp-Chair of General and Inorganic Chemistry, Saarland University
Am Markt, Zeile 1, GER-66125, Saarbrücken-Dudweiler
Unsaturated silicon clusters are plausible transient intermediates during the gas phase
deposition of silicon materials. Cluster-like assemblies in hydrogen-rich amorphous
silicon are thought to be band-gap determining.[1] The targeted syntheses of stable
unsaturated silicon clusters (siliconoids) has been a challenging goal.[2] Recently, we
reported that reduction of cyclotrisilane 1 yields the dismutational hexasilabenzene
isomer 2[3] which can be isomerized to propellane 3, the assumed global minimum on
the Si6R6 potential energy surface (Figure 1). Here we report on the functionalization
of the Si6 cluster backbone and its successful transfer to a variety of different
substrates.
Figure 1. Syntheses of hexasilabenzene isomer 2, propellane 3.
References:
[1] Y. S. Shcherbyna, T. V. Torchynska, Thin Solid Films, 2010, 518, 204.
[2] (a) D. Scheschkewitz, Angew. Chem. Int. Ed. 2005, 44, 2954; (b) G. Fischer, V. Huch, P. Mayer, S.
Vasisht, M. Veith, N. Wiberg, Angew. Chem. Int. Ed., 2005, 44, 7884; (c) D. Nied, R. Köppe, W.
Klopper, H. Schnöckel, F. J. Breher, J. Am. Chem. Soc., 2010,132, 10264; (d) K. Abersfelder, A.
Russell, H. S. Rzepa, A. J. P. White, P. R. Haycock, D. Scheschkewitz, J. Am. Chem. Soc., 2012, 134,
16008; (e) A. Tsurusaki, C. Iizuka, K. Otsuka, K., S. Kyushin, J. Am. Chem. Soc., 2013, 135, 16340.
[3] K. Abersfelder, A. J. P. White, H. S. Rzepa, D. Scheschkewitz, Science 2010, 327, 564.
[4] K. Abersfelder, A. J. P. White, R. J. F. Berger, H. S. Rzepa, D. Scheschkewitz, Angew. Chem. Int.
Ed. 2011, 50, 7936.
Poster presentation - P035
Synthesis and Characterization of Cyclic Acylsilanes - Precursors for
Brook-Type Cyclic Silenes
Michael Haas, Harald Stüger and Christa Grogger
christa.grogger@tugraz.at
TU Graz, Institute of Inorganic Chemistry
Stremayrgasse 9, 8010 Graz, Austria
Cyclic acylsilanes are versatile starting materials for the formation of previously
unknown Brook-type cyclic silenes.[1] They can be synthesized in good yields
(> 60 %) by a 2-step process, involving the formation of potassium silanides 2a-d
from 1,1,4,4-tetrakis(trimethylsilyl)cyclohexasilane 1 and their subsequent reaction
with acyl chlorides. Compounds 3a-d were isolated and characterized by X-ray data
analysis, UV/Vis- spectroscopy and cyclic voltammetry.
Figure 1. Formation of Cyclic Acylsilanes
References:
[1] (a) Stueger, H.; Hasken, B.; Haas, M.; Rausch, M.; Fischer, R.; Torvisco, A. Organometallics 2014,
33, 231; (b) Haas, M.; Fischer, R.; Flock, M.; Mueller, S.; Rausch, M.; Saf, R.; Torvisco, A.; Stueger,
H. Organometallics 2014, 33, 5956.
Poster presentation - P036
2-(Dimethylaminomethyl)-ferrocenyl Substituted Silanols,
Disilanolates and Siloxanes: Search for new Intermediates
Christopher Golz, Carsten Strohmann*
christopher.golz@tu-dortmund.de
Faculty of Chemistry and Chemical Biology, TU Dortmund University
Otto-Hahn-Str. 6, Ger-44227, Dortmund
2-(Dimethylaminomethyl)-ferrocenyl substituted silanols represent a highly promising
substance class. Due to the high steric hindrance of the ferrocene and/or the
intramolecular hydrogen bonds to the amino-group, these silanols are comparatively
stable in terms of condensation reactions. For the disiloxandiol, only one diastereomer
was observed, in which the configuration of the silicon centers is dependent on the
planar chiral ferrocenyl-substituents. The synthesis of the enantiopure compound is
possible via the (Sp)‑ferrocenyllithium.[1] The cleavage of siloxanes with zinc salts or
the deprotonation of silanols resulting in stable silanolates were both observed in our
group.[2] Even more interesting is the hydrolysis of the methoxysilanes in the presence
of zinc salts, leading to the unexpected isolation of partially hydrolyzed
methoxysilanolates, granting an unique insight into the mechanism of the hydrolysis
reaction of silicon compounds.
Figure 1. Disiloxandiols and silandiols derived from ferrocenyl substituted methoxysilane.
Acknowledgements: We are grateful to the Deutsche Forschungsgemeinschaft (DFG) and Fonds der
Chemischen Industrie (FCI) for financial support.
References:
[1] P. Steffen, C. Unkelbach, M. Christmann, W. Hiller, C. Strohmann, Angew. Chem. Int. Ed. 2013,
52, 9836-9840.
[2] (a) C. Däschlein, C. Strohmann, Z. Naturforsch. 2009, 64b, 1558-1566; (b) C. Däschlein, J. O.
Bauer, C. Strohmann, Angew. Chem. 2009, 121, 8218-8221.
Poster presentation - P037
Synthesis and Structure of a Stable 1,2-Digermabenzene
Tomohiro Sugahara, Takahiro Sasamori, Tomohiro Agou, Jing-Dong Guo, Shigeru
Nagase, and Norihiro Tokitoh
sugahara@boc.kuicr.kyoto-u.ac.jp
Institute for Chemical Research and Fukui Institute for Fundamental Chemistry,
Kyoto Univ.
Gokasho, Uji, Kyoto 611-0011, Japan
The replacement of carbon atoms in the benzene ring with heavier group 14 elements,
generating „heavy aromatics“, has attracted many chemists as unique π conjugated
ring system. However, this class of compounds is known to be highly susceptible
toward the addition reaction with moisture and/or aerobic oxygen and selfoligomerization. Nowadays, many examples of the stable heavy aromatics have been
synthesized by using bulky substituents with keeping their intrinsic nature of
reactivity. The synthesis of stable 1,2-disilabenzenes, for example, has been
accomplished by the reaction of stable disilynes with alkynes.[1] These compounds
have generated great interest, especially with respect to their properties as a cyclic 6πconjugated system including a Ge=Ge moiety. Here, we will report the synthesis and
isolation of the 1,2-digermabenzene via the reaction of a digermyne, TbbGeGeTbb
(Tbb = 4-t-Bu-2,6-[CH(SiMe3)2]-C6H2), with two equivalents of acetylene.[2] In
addition, the chemical properties, the physical properties and theoretical calculations
of the obtained 1,2-digermabenzene will also be described.
References:
[1] (a) R. Kinjo, M. Ichinohe, A. Sekiguchi, N. Takagi, M. Sumimoto, S. Nagase, J. Am. Chem. Soc.
2007, 129, 7766; (b) J. S. Han, T. Sasamori, Y. Mizuhata, N. Tokitoh, Dalton Trans. 2010, 39, 9238.
[2] T. Sasamori, T. Sugahara, T. Agou, J. Guo, S. Nagase, R. Streubel, N. Tokitoh, Organometallics
2015, in press. [DOI: 10.1021/om501204u]
Poster presentation - P038
Sila- and Germacyclopentadienyl Radicals vs. Anions
Crispin R. W. Reinhold, Thomas Müller*
crispin.reinhold@uni-oldenburg.de
Institute of Chemistry, Carl von Ossietzky University of Oldenburg
Carl von Ossietzky Str. 9 - 11, 26129 Oldenburg, Federal Republic of Germany
Sila- and germacyclopentadienes[1] (siloles and germoles) show remarkable electronic
and photo physical properties.[2] By creating localized spin centres in those
heterocycles, interesting functionalities could be added. Especially the integration of
those systems into macromolecules would lead to cooperative effects.[3] Against this
background we reduced 1-halogenated siloles and germoles and obtained respective
radicals. Further reduction of the germole led to the expected mono anion. In the case
of the silole a dimeric dianion is formed. The EPR spectra of the radicals and the
molecular structures of the anions will be presented.
Figure 1. Reduction of halogenated siloles and germoles to radicals and anions.
Acknowledgements: Special thanks to Dr. Boris Tumanskii, Dr. Dmitri Bravo-Zhivotovskii and Prof.
Yitzhak Apeloig. This work was supported by the Carl von Ossietzky University of Oldenburg.
References:
[1] J. Dubac, A. Laporterie, G. Manuel, Chem. Rev. 1990, 90, 215.
[2] S. Yamaguchi, K. Tamao, J. Chem. Soc., Dalton Trans. 1998, 3693.
[3] T. Nozawa, M. Nagata, M. Ichinohe, A. Sekiguchi, J. Am. Chem. Soc. 2011, 133, 5773.
Poster presentation - P039
Photochemical Reactivity of Cyclic Acylgermanes
Dominik Schnalzer, Michael Haas, Ana Torvisco and Harald Stueger*
dominik.schnalzer@student.tugraz.at
Institute of Inorganic Chemistry
Institute for Inorganic Chemistry Graz University of Technology Stremayrgasse 9/V
A-8010 Graz, Austria
The reactivity of acylgermanes differs from that of acylsilanes due the fact that the
acylgermanes do not undergo Brook-type rearrangement reactions.[1] Instead, upon
irradiation, acylgermanes predominantly react via Norrish type-Ι cleavage of the
germanium-carbon bond[2-4] to give complex product mixtures in the case of acyclic
substrates because of extensive follow-up reactions of the initially formed germyl
radicals.[5] In contrast, the newly synthesized cyclic acylgermanes 1a-c mainly
afforded the Ge-Ge coupling product 2 after irradiation with λ > 300 nm light, which
can be explained by the enhanced stability of the cyclic germyl radical 3. The
previously unknown compound 2 was isolated and fully characterized
spectroscopically and by single crystal X-ray crystallography. Further studies to
enlarge the scope of this new method for the formation of Ge-Ge bonds are currently
underway.
Figure 1. Irradiation of acylgermanes.
References:
[1] A. G. Brook, Acc. Chem. Res., 1974, 7, 77.
[2] K. Mochida, K. Ichikawa, S. Okui, Y. Sakaguchi, H. Hayashi, Chem. Lett., 1985, 1433.
[3] M. B. Taraban,; V. I. Maryasova,; T.V. Leshina,; L. I. Rybin,; D. V. Gendin,; N.S. Vyazankin, J.
Organomet. Chem., 1987 326,347.
[4] S. Kiyooka,; M. Hamada,; H. Matsue,; M. Hamada,; R. Fujiyama, , J. Org. Chem., 1990 55, 5562.
[5] A. G. Brook,; F. Abdesaken; H. Söllradl, J. Organomet. Chem., 1986, 299, 9-13.
Poster presentation - P040
Synthesis and Characterization of the first relatively stable
Germenolates
Michael Haas, Dominik Schnalzer, Ana Torvisco and Harald Stueger
michael.haas@tugraz.at
Institute of Inorganic Chemistry, Graz University of Technology
Stremayrgasse 9, 8010 Graz, Austria
Enolates and silenolates are widely employed in organic as well as in inorganic
chemistry.[1,2] However, the synthesis and characterization of germenolates was
neglected. To the best of our knowledge only one study concerning germenolates has
been published in literature by the group of Bravo-Zhivotovskii.[3] As we have
reported earlier, it is possible to synthesize and characterize cyclic silenolates and
react them with electrophiles.[4] Due to the fact that these cyclic silenolates exhibit
increased stability in comparison to the acyclic derivatives, it was obvious to attempt
the synthesis of the less stable germenolates. In this lecture we discuss the synthesis,
spectroscopic characterization and molecular structures of the first cyclic
germenolates 1a-c and the conversion of 1a,b to germene 2a,b.
Figure 1. Synthesized cyclic Germenolates and Germenes
Acknowledgements: NAWI-Graz shall be gratefully acknowledged for financial support
References:
[1] For general reviews about enolates, see e. g.: (a) D. Stolz, U. Kazmaier in The Chemistry of Metal
Enolates, Part 1 (Eds.: Z. Rappoport, J. Zabicky), Wiley, Hoboken, 2009, pp. 355-411; (b) D. Seebach,
Angew. Chem. 1988, 100, 1685-1715; Angew. Chem. Int. Ed. Engl. 1988, 27, 1624-1654; (c) P. Veya,
C. Floriani, A. Chiessi-Villa, C. Rizzoli, Organometallics 1994, 13, 214-223.
[2] For example see: (a) J. Ohshita, S. Masaoka, Y. Masaoka, H. Hasebe, M. Ishikawa, A. Tachibana,
T. Yano, T. Yamabe, Organometallics 1996, 15, 3136; (b) T. Guliashvili, I. El-Syed, A. Fischer, H.
Ottosson, Angew. Chem. Int. Ed. 2003, 42, 1640; (c) R. Dobrovetsky, L. Zborovsky, D. Sheberla, M.
Botoshansky, D. Bravo-Zhivotovskii, Y. Apeloig, Angew. Chem. Int. Ed. 2010, 49, 4084.
[3] I. S. Biltueva, D. A. Bravo-Zhivotovskii, I. D. Kalikhman, V. Yu. Vitkovskii, S. G. Shevchenko, N.
S. Vyazankin, M. G. Voronkov, J. Organomet. Chem. 1989, 368, 163.
[4] M. Haas, R. Fischer, M. Flock, S. Mueller, M. Rausch, S. Saf, A. Torvisco, H. Stueger,
Organometallics 2014, 33, 5956.
Poster presentation - P041
Cationic Rearrangements in Polysilanes and Polygermasilanes Subtle Capture of Intermediates
Lena Albers, Thomas Müller*
Lena.albers@uni-oldenburg.de
Institute of Chemistry, Carl von Ossietzky University Oldenburg
Carl von Ossietzky Strasse 9-11, 26129 Oldenburg, Federal Republic of Germany
Linear, permethylated polysilanes[1,2] and polygermasilanes[3,4] always transform in a
Lewis acid catalysed Wagner-Meerwein analogue rearrangement, via methyl or
trimethylsilyl shifts, into their branched isomers to obtain quaternary* silicon or
germanium atoms. Our investigations on Lewis acid catalysed rearrangements in
polysilanes and polygermasilanes give astonishing insights into silyl cation chemistry.
We use hydrogen substituted polysilanes and polygermasilanes to define the position
of the initial positively charged atom by hydride transfer reaction to investigate the
reaction mechanism. Cationic intermediates of these rearrangements were captured by
the formation of Si-H-Si bridges. This structural motif[5,6] is evidenced by low
temperature NMR spectroscopy and quantum mechanical calculations. By this means
we are able to propose reaction mechanisms of Lewis acid catalysed rearrangements
of polysilanes and polygermasilanes.
Figure 1. Stabilisation of cationic intermediates by Si-H-Si bridges.
* quaternary = Si or Ge atom substituted with 4 silyl groups
Acknowledgements: This work was supported by the ERA-chemistry program (DFG-Mu1440/8-1,
FWF-I00669).
References:
[1] M. Ishikawa, J. Iyoda, H. Ikeda, K. Kotake, T. Hashimoto, M. Kumada, J. Am. Chem. Soc. 1981,
103, 4845.
[2] H. Wagner, A. Wallner, J. Fischer, M. Flock, J. Baumgartner, C. Marschner, Organometallics 2007,
26, 6704‑6717.
[3] H. Wagner, J. Baumgartner, T. Müller, C. Marschner, J. Am. Chem. Soc. 2009, 131, 5022.
[4] S. Sharma, N. Caballero, H. Li, K. H. Pannell, Organometallics 1999, 18, 2855.
[5] T. Müller, Angew. Chem. 2001, 113, 3123-3126.
[6] A. Sekiguchi, Y. Murakami, N. Fukaya, Y. Kabe, Chem. Lett. 2004, 33, 530-531
Poster presentation - P042
Is Me3SiOK a Substitute for Me3COK in Schlosser’s Base Mixtures?
Kathrin Louven, Stephan G. Koller, Carsten Strohmann*
kathrin.louven@tu-dortmund.de
Faculty of Chemistry and Chemical Biology, TU Dortmund University
Otto-Hahn-Str. 6, GER-44227, Dortmund
The use of Schlosser’s Base Mixtures is an elegant method for metalation reactions at
low temperatures. Organolithium reagents are combined with potassiumalkoxides
forming the reactive superbasic “ IC OR” species.[1,2] The main focus of the
presented research lies on the identification of further Schlosser’s Base like systems.
Potassiumalkoxide is substituted by potassiumsilanolate and the corresponding
reactivity and selectivity is tested on deprotonations. Furthermore, aggregates formed
in the Schlosser’s Base Mixtures t-BuLi/Me3COK and t-BuLi/Me3SiOK will be
compared. The two aggregates of the formula [(Me3ElO)8K4Li4(THF)4] show
different arrangements of the Li- and K-centers for El = C and El = Si. Further
examples will be discussed.
Figure 1. Isolated aggregates of [(Me3ElO)8K4Li4(THF)4]; El = C, Si.[3]
Acknowledgements: We are grateful to the Deutsche Forschungsgemeinschaft (DFG) for financial
support.
References:
[1] M. Schlosser, Pure & Appl. Chem 1988, 60, 1627-1634.
[2] C. Unkelbach, D. F. O’Shea, C. Strohmann, Angew. Chem. Int. Ed. 2014, 53, 553-556.
[3] W. Clegg, A. M. Drummond, S. T. Liddle, R. E. Mulvey, A. Robertson, Chem. Comm. 1999, 16,
1569-1570 (prepared from t-BuOLi/t-BuOK).
Poster presentation - P043
Syntheses and Reactions of Cationic 4-Phosphonio Substituted NHCs
Kai Schwedtmann, Robin Schoemaker, Felix Hennersdorf, Jan J. Weigand
kai.schwedtmann@chemie.tu-dresden.de
Department of Chemistry and Food Chemistry , University of Technology Dresden
Mommsenstrasse 4, 01062 Dresden, Germany
The use of N-heterocyclic carbenes (NHCs) in phosphorus chemistry has led to some
remarkable discoveries with considerable impact in recent years. Only a handful of
examples are known where the 4-position of certain NHCs can be selectively
addressed leading to 4-phosphanyl substituted imidazolium salts or NHCs in the
presence of chlorophosphanes[1,2a] or phosphaalkenes.[2b] In this context we present a
new and facile concept for the synthesis of 4-phosphanyl substituted imidazolium
triflates 1[OTf]. Subsequent functionalization leads to cationic 4-phosphonio
substituted NHCs 3[OTf] exhibiting a Lewis acidic and a Lewis basic moiety which
can be used in follow up chemistry.
Figure 1. Preparation of cationic 4-phosphonio substituted NHCs 3[OTf].
References:
[1] K. Schwedtmann, M. H. Holthausen, K.-O. Feldmann, Jan J. Weigand, Angew. Chem. Int. Ed.
2013, 125, 14204.
[2] a) D. Mendoza-Espinosa, B. Donnadieu, G. Bertrand, J. Am. Chem. Soc. 2010, 132, 7264; b) J. I.
Bates, P. Kennepohl, D. P. Gates, Angew. Chem. Int. Ed. 2009, 48, 9844.
Poster presentation - P044
Synthesis and Reactivity of Ditopic Carbanionic N-Heterocyclic
Carbene Complexes
Jordan B. Waters*, Lajoy S. Tucker and Jose M. Goicoechea
Jordan.waters@chem.ox.ac.uk
Department of Chemistry, Chemistry Research Laboratory, University of Oxford
12 Mansfield Rd, Oxford, OX1 3TA, UK
Since the discovery of the first isolable N-heterocyclic carbene (NHC) 24 years ago,[1]
these compounds have gone from chemical curiosities to ubiquitous ligands in
modern organometallic chemistry. NHCs can bond to metals through the
“conventional” (C2) or “abnormal” (C ) positions.[2] Recently, Robinson reported the
synthesis of the first N-heterocyclic “dicarbene” (NHDC), by deprotonation of an
NHC resulting in a species capable of binding through the C2 and C4 positions
simultaneously.[3] Accordingly, we have recently reviewed the known chemistry of
ditopic carbanionic NHCs.[4] We have been investigating the reactivity of the lithium
salt of the deprotonated IPr carbene towards E[N(SiMe3)2]2 complexes (E = Ge, Sn,
Pb). Such reactions in an equimolar ratio result in the formation of novel germylene,
stannylene or plumbylene species. We have also synthesised the analogous potassium
salt (KIPr) and studied the reactivity towards EE[N(SiMe3)2]2 (E = Ge, Sn, Pb and
Zn).[5]
The
products
are
all
C4
bonded
adducts
i
E[:CCH{[N(2,6- Pr2C6H3)]2C:}]E[N(SiMe3)2]2]− which in the case for E = Ge and Pb,
will slowly rearrange to afford the bis-carbene adduct along with the homoleptic
metal tris-amide (see Figure).
References:
[1] Arduengo, A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc., 1991, 113, 361–363.
[2] Aldeco-Perez, E.; Rosenthal, A. J.; Donnadieu, B.; Parameswaran, P.; Frenking, G.; Bertrand, G.
Science, 2009, 326, 556–559.
[3] Wang, Y.; Xie, Y.; Abraham, M. Y.; Wei, P.; Schaefer, H. F.; Schleyer, P. v. R.; Robinson, G. H. J.
Am. Chem. Soc., 2010, 132, 14370–14372.
[4] Waters, J. B. Goicoechea, J. M. Coord. Chem. Rev., 2014, DOI: 10.1016/j.ccr.2014.09.020
[5] Waters, J. B.; Goicoechea, J. M. Dalton Trans., 2014, 43, 14239.
Poster presentation - P045
Reactivity of heavier NHC-coordinated Vinylidene Analogues
towards Anionic Nucleophiles
David Nieder, Anukul Jana, Volker Huch, David Scheschkewitz*
david.nieder@uni-saarland.de
Krupp-Chair of General and Inorganic Chemistry, Saarland University
Am Markt Zeile 1, GER-66125, Saarbrücken-Dudweiler
Vinylidene is the only electron precise isomer of acetylene, but so far derivatives have
only been observed in cold matrices and as ligands in transition metal complexes.[1]
Recently, we reported on the synthesis of the first two isolable heavier versions of
vinylidene as donor-acceptor complexes with an N-heterocyclic carbene (1 and 2).[2]
The two highly functionalized molecules (double bond between Si and Ge, lone pair
at the GeII-center, base coordination) provide various opportunities for further
manipulation, e.g. the reaction of 1 with phenylacetylene leading to a base-stabilized
cyclic germylene and 2 with mesityl lithium resulting in NHC-coordinated heavier
cyclopropylidenes after LiCl elimination.[2,3] These results prompted us to further
investigate the behavior of silagermenylidene 2 towards other, differently sized,
anionic nucleophiles. The various low valent germanium systems thus obtained will
be discussed here.
Figure 1. Heavier NHC-coordinated vinylidenes 1 and 2.
References:
[1] H.- Y. Liao, M.- D. Su, S.- Y Chu, Inorg. Chem., 2000, 39, 3522.
[2] (a) A. Jana, V. Huch, D. Scheschkewitz, Angew. Chem., 2013, 125, 12401; (b) A. Jana, M.
Majumdar, V. Huch, M. Zimmer, D. Scheschkewitz, Dalton Trans., 2014, 43, 5175.
[3] (a) A. Jana, V. Huch, H. S. Rzepa, D. Scheschkewitz, Angew. Chem. Int. Ed., 2014, 54, 289; (b) A.
Jana, I. Omlor, V. Huch, H. S. Rzepa, D. Scheschkewitz, Angew. Chem., 2014, 126, 10112.
Poster presentation - P046
Stability and Structure of Ferrocene based Carbene Analogues
Zsolt elemen, Zoltán Benkő, Dénes Szieberth, Rudolf Pietschnig, Dietrich Gudat,
László Nyulászi
kelemen.zsolt@mail.bme.hu
Budapest University of Technology and Economics, Department of Inorganic and
Analytical Chemistry
Szt Gellért tér 4. H-1111 Budapest, Hungary
The chemistry of stable carbenes is of current interest. While the most frequently
investigated carbenes are N-heterocyclic carbenes (NHC), among them particularly
imidazole-2-ylidenes (1, E 1 = E2: NR; E’: C:), recently a ferrocene based carbene 2
(E 1 = E2: NAd, E’: C:) has been reported as a stable compound (Figure 1).1 Electronic
structure calculations indicated an increased singlet-triplet gap of 2 (E1 = E2: NH, E’:
C:) with respect to (Me2N)2C, indicating a stabilization.2 In the present work we
investigate the stability of analogues of 2 (E1: NH, PH, S, O; E’: C, Si, P+ and N+) by
density functional calculations, using the isodesmic reaction (Figure 1). Comparision
with the analogous NCHs, show that 2 type structures exhibit smaller, but still
significant stabilization. Details of the electronic structure and the possible interaction
between E2 and Fe throughout the investigated series will also be discussed.
Figure 1. Investigated systems E1: O, S, NR, PR; E2: C, Si, PR and the isodesmic reaction.
References:
1 U. Siemeling, C. Farber C. Bruhn Chem. Commun., 2009, 98–100; see also D. M. Khramov, E. L.
Rosen, V. M. Lynch, C. W. Bielawski Angew. Chem. Int. Ed. 2008, 47, 2267 –2270.
2 C. Goedecke, M. Leibold, U. Siemeling, G. Frenking J. Am. Chem. Soc. 2011, 133, 3557–3569.
Poster presentation - P047
Acyclic Two-Coordinate Cationic Germylenes – Metal Element Bond
Formation
Arnab Rit, Simon Aldridge*
arnab.rit@chem.ox.ac.uk
Chemistry Research Laboratory, University of Oxford
Mansfield road, OX1 3TA, Oxford
The chemistry of thermally stable divalent neutral germanium compounds has
attracted a lot of attention in recent years.[1] In contrast to neutral compounds, :GeX2,
related cationic germanium(II) species of the type [:Ge(L)X]+ are relatively rare.[2]
Given recent interest in comparisons of fundamental properties between carbon and
its heavier congeners, understanding the structure and reactivity of cationic
germylenes might open up many interesting areas as has been seen for the
corresponding carbenium ions. In addition, the presence of a cationic charge may lead
to the isolation of unsaturated monomeric species (e.g. containing Ge=E multiple
bonds) by discouraging the sorts of oligomerization processes seen for neutral
analogues. Herein we present the synthesis of rare acyclic two-coordinate cationic
germylenes by chloride abstraction from NHC-stabilized chlorogermylenes. Steric
and electronic tuning of the substituents at germanium allows control of aggregation.
Thus, smaller NHCs result in dimerization to give novel dicationic digermenes
[X(L)Ge=GeX(L)]2+. Bulkier substituents yield monocationic germylenes which react
cleanly with azido or diazo compounds under N2 release to give monomeric imido or
alkylidene complexes.
Figure 1. Two-coordinate cationic germylenes and subsequent metal element bond formation.
Acknowledgements: European Commission is gratefully acknowledged for a Marie Curie postdoctoral grant to A.R.
References:
[1] (a) O. Kühl, Coord. Chem. Rev., 2004, 248, 411; (b) Z. Rappoport, The Chemistry of Organic
Germanium, tin and lead compounds; Wiley: Chichester, 2002; Vol. 2, p. 284-332.
[2] (a) H. V. R. Dias, Z. Wang, J. Am. Chem. Soc., 1997, 119, 4650; (b) M. Stender, A. D. Phillips, P.
P. Power, Inorg. Chem., 2001, 40, 5314.
Poster presentation - P048
Ferrocene-based Tetrylenes
Jan Oetzel, Clemens Bruhn, Ulrich Siemeling*
jan.oetzel@uni-kassel.de
Institute of Chemistry, University of Kassel
Heinrich-Plett-Straße 40, GER-34117, Kassel
Soon after the spectacular isolation of the first stable N-heterocyclic carbene (NHC)
by Arduengo et al. in 1991, NHCs and related diaminocarbenes attained the status of
ordinary compounds with very useful, but essentially unspectacular, chemical
behavior.[1] In contrast to this widespread judgement, ferrocene-based NHCs of type
1a (Fig.) exhibit a highly unexpected reactivity, especially towards small molecules
like CO or NH3.[2] We expect unusual properties for the heavier homologues of NHC
1a, too. The aim of this research is to synthesize and study ferrocene-based Nheterocyclic silylenes (1b) and also germylenes (1c), stannylenes (1d) and
plumbylenes (1e; Fig.). The reaction of di-li-thi-ated 1,1’-diaminoferrocenes (2) with
SiX4 (X = Br, Cl) affords NHSi precursors (3), which need to be reduced in the final
step. Corresponding NHGe, NHSn or NHPb can be synthesized by reaction of 2 with
[GeCl2(dioxane)], SnCl2or PbCl2 (Fig.). However, the reduction of NHSi precursors 3
(R = neopentyl, TMS) turned out to be a tough challenge, prompting us to investigate
the use of a silicon(II) precursor. Gratifyingly, we found that the corresponding
silylenoid of 1b can be generated by reaction of 2 with [SiCl2(nhc)][3]. The NHGe 1c
(R = neopentyl, TMS) and the NHSn 1d (R = TMS) have been synthesized and fully
characterized. The attempted synthesis of NHPb 1e led to a fascinating complex
containing three Pb atoms.
Figure 1. NHC system 1a[2] and routes to corresponding N-heterocyclic silylenes (1b),
germylenes (1c), stannylenes (1d) and plumbylenes (1e); Fc = 1,1’-ferrocenediyl.
References:
[1] (a) F. E. Hahn, M. C. Jahnke, Angew. Chem. Int. Ed. 2008, 47, 3122; (b) M. N. Hopkinson, C.
Richter, M. Schedler, F. Glorius, Nature 2014, 510, 485.
[2] U. Siemeling, C. Färber, C. Bruhn, M. Leibold, D. Selent, W. Baumann, M. von Hopff-gar-ten, C.
Goedecke, G. Frenking, Chem. Sci. 2010, 1, 697.
[3] R. S. Ghadwal, H. W. Roesky, S. Merkel, J. Henn, D. Stalke, Angew. Chem. 2009, 121, 5793.
Poster presentation - P049
Cyclic distannene in reaction with terminal alkynes
Jessica Edrich, Jens Henning, Lars Wesemann*
jessica.edrich@student.uni-tuebingen.de
Institut für Anorganische Chemie, Universität Tübingen
Auf der Morgenstelle 18, 72076 Tübingen, Germany
Since the first distannene featuring a formal tin-tin double bond was characterized by
Lappert and co-workers in 1976[1], the field of multiple bonding between heavier
group 14 elements attracted great attention. Herein, we present the cyclic distannene 1
(Figure 1) in which the two tin atoms are linked to a 9,9-dimethylxanthene backbone
and are sterically protected by two bulky m-terphenyl moieties (ArMes = C6H3-2,6Mes2, Mes = C6H2-2,4,6-Me3)[2]. These m-terphenyl ligands were introduced by
Power and co-workers into low-valent main group element chemistry[3,4]. Increasing
the steric demand on the m-terphenyl substituents yields compound 2 (ArTrip = C6H32,6-Trip2, Trip = C6H2-2,4,6-i-Pr3)[5]. Compound 2 shows no tin-tin interaction in the
solid state, the backbone is planar and not folded to facilitate a shorter tin-tin distance
like in case of distannene 1. Hence, 2 can be categorized as bis(stannylene). To
compare their reactivity, they were reacted with terminal alkynes. The reaction of 1
and 2 with phenylacetylene yield the 1,2-distannacyclobut-3-enes 3 and 4. While the
reaction of 1 to 3 is irreversible, the reaction of 2 to 4 shows reversibility at room
temperature.
Figure 1. Reaction of distannene 1 and bis(stannylene) 2 with phenylacetylene.
References:
[1] P. J. Davidson, D. H. Harris, M. F. Lappert, J. Chem. Soc. Dalton Trans. 1976, 2268–2274.
[2] J. Henning, L. Wesemann, Angew. Chem. Int. Ed. 2012, 51, 12869–12873.
[3] K. Ruhlandt-Senge, J. J. Ellison, R. J. Wehmschulte, F. Pauer, P. P. Power, J. Am. Chem. Soc.
1993, 115, 11353–11357.
[4] L. Pu, A. D. Phillips, A. F. Richards, M. Stender, R. S. Simons, M. M. Olmstead, P. P. Power, J.
Am. Chem. Soc. 2003, 125, 11626–11636.
[5] J. Henning, K. Eichele, R. F. Fink, L. Wesemann, Organometallics 2014, 33, 3904–3918.
Poster presentation - P050
Reductive Cleavage of the CO Triple Bond by an Anionic Lowvalent
Maingroup Species
Cem B. Yildiz, Moumita Majumdar, Isabell Omlor, Akin Azizoglu, Volker Huch,
David Scheschkewitz*
cemburak.yildiz@uni-saarland.de
Krupp-Chair of General and Inorganic Chemistry, Saarland University
66125 Saarbrücken-Dudweiler, Germany
The reduction of carbon monoxide is of considerable interest in the context of C1
chemical feedstocks of non-fossil origin[1]. The Fischer-Tropsch process for the
production of hydrocarbons from CO requires transition metals as heterogeneous
catalyst. In addition, numerous studies employ homogeneous transition metal
complexes to achieve complete cleavage of the CO triple bond[2]. Recently, a few
maingroup systems have been shown to activate carbon monoxide
stoichiometrically[3]. For instance, the direct carbonylation of cyclotrisilenes without
cleavage of the C≡O bond was reported by Sekiguchi and Scheschkewitz [4]. Here we
report complete reductive cleavage of the triple bond in carbon monoxide by a lithium
disilenide under milder conditions. The product with a cyclic Si2O2 motif at the center
is isolated in almost quantitative yield. The mechanism of this seemingly complex
reaction is addressed on the basis of DFT computations as well as experimentally by
preparative studies involving Group 6 metal carbonyls.
Figure 1. Room temperature reductive coupling of CO by lithium disilenide.
References:
[1] (a) V. Macho, M. Kralik, L. Komora, Pet. Coal, 1997, 39, 6. (b) P. M. Maitlis, J. Organomet.
Chem. 2004, 689, 4366 (c) N. M. West, A. J. M. Miller, J. A. Labinger, J. E. Bercaw, Coord. Chem.
Rev. 2011, 255, 881. (d) C. J. Cramer, J. Chem. Soc. Perkin Trans., 1998, 2, 1007.
[2] C. Alessandro, E. Solari, R. Scopelliti, C. Floriani, J. Am. Chem. Soc. 2000, 122, 538.
[3] (a) H. Braunschweig, T. Dellermann, R. D. Dewhurst, W. C. Ewing, K. Hammond, J. O. C.
Jimenez-Halla, T. Kramer, I. Krummenacher, J. Mies, A. K. Phukan, A. Vargas, Nat. Chem. 2013, 5,
1025. (b) X. Wang, Z. Zhu, Y. Peng, H. Lei, J. C. Fettinger, P. P. Power, J. Am. Chem. Soc.2009, 131,
6912.
[4] (a) M. J. Cowley, Y. Ohmori, V. Huch, M. Ichinohe, A. Sekiguchi, D. Scheschkewitz, Angew.
Chem. 2013, 125, 13489; Angew. Chem. Int. Ed. 2013, 52, 13247. (b) M. J. Cowley, V. Huch, D.
Scheschkewitz, Chem. Eur. J. 2014, 20, 9221.
Poster presentation - P051
A Computational Chemistry Quest for Viable and Stable Tin(0)
Compounds, The Stannylones.
Jan Turek,(a) Aleš Růžička,(b) Frank De Proft(a)
jturek@vub.ac.be
Research Group of General Chemistry (ALGC), Member of the QCMM VUB-UGent
Alliance Research Group, Vrije Universiteit Brussel (VUB),
Pleinlaan 2, 1050 Brussels, Belgium
(b)Department of General and Inorganic Chemistry, Faculty of Chemical
Technology, University of Patrdubice
The chemistry of heavier low-valent Group 14 elements has recently attracted
considerable attention in the field of main group metal chemistry. This research has
not only produced various interesting compounds,[1] but has also made it possible to
demonstrate that some of these low-valent Group 14 derivatives can activate small
molecules under mild conditions and display promising catalytic properties for future
applications.[2] Among the low-valent Group 14 derivatives, monoatomic zero
oxidation state complexes are perhaps the most fascinating.[3] The main objective of
the presented work is the theoretical investigation of the structure, bonding and
reactivity of a series of new unprecedented compounds where the Sn atom is present
with a formal oxidation state of 0. Particular attention is focused on the stabilization
effect of the hybrid N-heterocyclic carbene (NHC) ligands containing both donor and
acceptor substituents (Figure 1).
Figure 1. Selected structural types of studied NHC-Sn(0) complexes.
Acknowledgements: The authors would like to acknowledge the generous financial support of FWO,
under the scheme FWO Pegasus Marie Curie fellowship.
References:
[1] (a) Y. Mizuhata, T. Sasamori, N. Tokitoh, Chem. Rev., 2009, 109, 3479; (b) Y. Wang, G. H.
Robinson, Chem. Commun., 2009, 5201; (c) C. Jones, Coord. Chem. Rev., 2010, 254, 1273; (d) P. P.
Power, Acc. Chem. Res., 2011, 44, 627; (d) M. Asay, C. Jones, M. Driess, Chem. Rev., 2011, 111, 354.
[2] P. P. Power, Nature, 2010, 463, 171.
[3] N. Takagi, T. Shimizu, G. Frenking, Chem. Eur. J., 2009, 15, 8593.
Poster presentation - P052
Functional Binary and Ternary Organotin Selenide Clusters
Niklas Rinn, Stefanie Dehnen*
Dehnen@chemie.uni-marburg.de
Department of Chemistry, Philipps University Marburg
Hans Meerwein Straße, GER-35039, Marburg
Organofunctionalized tin chalcogenide clusters have shown a multitude of
extraordinary properties, sparking the interest of the chemical community.[1−3]
Discreet functionalized Sn/Se Cluster could be synthesized in our group by
condensing R1SnCl3 (A, R1 = CMe2CH2C(O)Me) with Se(SiMe3)2 (B), leading to
[(SnR1)3Se4Cl] (1) or [(SnR1)4Se6] (2) depending on the solvent and A/B ratio.[4] By
adding transition metal salts M(PPh3)xCly (M = Cu, Ag, Pd) to 1 and 2 with additional
equivalents of B, the inorganic core rearranges and incorporates M to form novel
ternary Sn/Se/M clusters [{(R1SnIV)2Se2}3{Cu(PPh3)}2{Cu2SnII}(µ3-Se)6] (3),
[(SnR1)4(SnCl)2(CuPPh3)2Se10]
(4)
[(R1Sn)2Se2(CuPPh3)2Se2]
(5)
and
1
[{(Se@Ag6)}@Ag8(µ-Se)12{(R Sn)2Se2}6] (6). When adding hydrazine hydrate to the
clusters
or
during
cluster
formation
further
compounds
2
2
[Pd(PPh3)2Pd(PPh3)ClSn(R Cl2)Se2]
(7,
R
=
CMe2CH2C(NNH2)Me),
2
IV
[Se2Pd(PPh3)2Pd(PPh3)SeH][SnCl3] (8) and [{(R Sn )2Se2}2{Cu(PPh3)}2{SnII}(µ3Se)4(µ-Se)2] (9).
Figure 1. molecular structures of 3, 6 and 7 (from left to right).
References:
[1] M. Bouška, . Dostál, Z. Padělková, A. yčka, S. Herres-Pawlis, K. Jurkschat, R. Jambor, Angew.
Chem. 2012, 124, 3 3 −3 0.
[2] J. P. Eußner, B. E. K. Barth, E. Leusmann, Z. You, N. Rinn, S. Dehnen, Chem. Eur. J. 2013, 19,
13792−13 02
Poster presentation - P053
Group 14 element pyramidanes: theoretical studies
Olga A. Gapurenko,1* Vladimir Ya. Lee,2 Ruslan M. Minyaev,1 Vladimir I. Minkin,1
Yuki Ito,2 Takahiko Meguro,2 Haruka Sugasawa,2 Akira Sekiguchi2
gapur@ipoc.sfedu.ru
(1) Institute of Physical and Organic Chemistry, Southern Federal University; (2)
Department of Chemistry, University of Tsukuba
(1) Stachki ave. 194/2, Rostov on Don 344090, Russian Federation; (2) Tsukuba,
Ibaraki 305-8571, Japan
Pyramidanes represent a group of the fundamental non-classical cage compounds.
All-carbon pyramidane 1 (E = E' = C) is well-known theoretically but not yet
synthesized. First heavy group 14 element pyramidanes 1 (E = C, E' = Ge, Sn; E = E'
= Ge) are experimentally realized and characterized very recently.[1] We present DFT
calculation of a full series of all group 14 element pyramidanes with different
substituents R (Figure 1). All pyramidanes with E = C, independently of R, are stable
[energy minima on potential energy surface (PES)]. Stability of heavy pyramidanes 1
(E = Si, Ge) is dictated by the size of R: from a third-order saddle point (R = H) to a
local minimum or a transition state (R = SiMetBu2) on PES. This fact, as well as steric
stabilization, is explained by electron density donation from R to pyramidal E‒E'
bonds that can be seen by the electron localization function analysis: basin population
of E‒E' bonds increases with growing R.
Figure 1. Group 14 element pyramidanes.
Acknowledgements: This work was supported by the Russian Foundation for Basic Research (14-0392101), Russian Scientific Schools (NSh-274.2014.3), and by the Japanese Society for the Promotion
of Science (24550038).
References:
[[1](a) V. Ya. Lee, Y. Ito, A. Sekiguchi, H. Gornitzka, O. A. Gapurenko, V. I. Minkin, R. M. Minyaev,
J. Am. Chem. Soc., 2013, 135, 8794; (b) V. Ya. Lee, Y. Ito, O. A. Gapurenko, A. Sekiguchi, V. I.
Minkin, R. M. Minyaev, H. Gornitzka, Angew. Chem. Int. Ed., 2015, 54, in press [DOI:
10.1002/anie.201500731].
Poster presentation - P054
Quantitative Understanding of Multimetallic Cluster Growth
Stefan Mitzinger*,(a) Lies Broekaert,(a,b) Werner Massa,(a) Jan Weigend,(b)
Stefanie Dehnen (a)
stefan.mitzinger@chemie.uni-marburg.de
(a) Department of Chemistry and Scientific Centre for Material Science, Philipps
University of Marburg, Hans-Meerwein-Straße, D-35043 Marburg, Germany
(b) Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-vonHelmholtz Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany.
The chemistry of homoatomic and binary intermetalloid Zintl anions has been
investigated for several decades.1 In most cases, the structural features of Zintl anions
can be explained with Wade-Mingos rules or the Zintl-Klemm concept.2 By extraction
of quaternary metallic phases containing K/Ge/As/MV (MV = V, Nb, Ta) with
ethylenediamine (en), a new class of multimetallic Zintl anions was synthesized under
encapsulation of electron-poor transition metals.3 In case of the extraction of a
K/Ge/As/Ta phase five new compounds were fully characterized within one reaction
allowing the elucidation of the stepwise formation of multimetallic clusters, based on
the crystal structures and complementary quantum chemical studies of the involved
clusters (Ge2As2)2–, (Ge7As2)2–, [Ta@Ge6As4]3–, [Ta@Ge8As4]3–, and [Ta@Ge8As6]3–.
The results can even be generalized for an entire family of multimetallic clusters.
Acknowledgements: We thank the Friedrich-Ebert-Stiftung for their continuing support of this PhD
project.
References:
[1] S. Scharfe, F. Kraus, S. Stegmaier, A. Schier, T. F. Fässler, Angew. Chem. Int. Ed. 2011, 50, 3630–
3670.
[2] W. Klemm, in Festkörperprobleme 3 (Ed.: F. Sauter), Springer, Heidelberg, 1964, pp. 233–251.; K.
Wade, Advances in Inorganic Chemistry and Radiochemistry 1976, 18, 1–66.
[3] S. Mitzinger, L. Broeckaert, W. Massa, F. Weigend, S. Dehnen, Chem. Commun. 2015, 51, 3866–
3869.
Poster presentation - P055
CHEMISTRY OF INTRAMOLECULARLY COORDINATED
STANNYLENES
R. Jambor*, M. Novák
roman.jambor@upce.cz
Department of General and Inorganic Chemistry
UNIVERSITY of PARDUBICE, Faculty of Chemical Technology, Studentská 95,
Pardubice, CZ-53210
A valuable method for increasing the understanding of intramolecular binding forces
is the investigations of heavy carbene analogues (R2E), their transition metal
complexes (LnM=ER2) and compounds that contain multiple bonds between heavier
main group elements (R2E=ER2, RE=ER, and L n M=ER where E = group 14 elements
Si, Ge, Sn and Pb).
As part of a comprehensive study on intramolecularly coordinated heteroleptic
organostannylenes RSnCl, we discuss here the synthesis of their transition metal
complexes as well as the synthesis of the organotin(I) species (Chart 1). [1]
The reactivity of mentioned compounds will be also presented.
chart 1
Acknowledgements: The authors would like to thank the Grant Agency of the Czech Republic (1507091S) for financial support.
References:
[1] Jambor, R.; Kasná, B.; Kirschner, K.N.; Schuermann, M.; Jurkschat, K. Angew. Chem. Int. Ed.
2008, 47, 1650.
Poster presentation - P056
Stereoselective approaches towards bisphosphano substituted
tetrylenes via [3]-ferrocenophanes
Denis Kargin, Rudolf Pietschnig*
denis.kargin@uni-kassel.de
Department of Chemistry, University of Kassel
Heinrich-Plett-Straße 40, Germany-34132, Kassel
Phosphorus bridged [n]-ferrocenophanes (n = 1, 2, 3; with n specifying the number of
covalently bound atoms tethering two cyclopentadienyl rings of ferrocene) are
attractive molecules for various purposes such as asymmetric catalysis[1] or metal
containing polymers[2]. The discovery of reactive, transient, low-valent silicon
compounds occurred almost half a century ago, but isolation of more stable Si(II)
derivatives in 1986 by Jutzi[3] and especially the N-heterocyclic derivative in 1994 by
West and Denk[4] attracted more attention to this interesting field. Subsequently this
lead to further research on new silylenes/silylenoids for reaction with small molecules
or for catalysis. Starting from the air and moisture stable compound I (R=tBu)
containing trivalent chiral phosphorus atoms, we obtained suitable precursors for
reduction processes or dehydrohalogenation II, exhibiting defined stereochemistry.
Currently we are aiming for free phosphorus substituted tetrylenes III incorporating
silicon, tin and germanium atoms linking two phosphorus atoms.
Figure 1. Phosphorus substituted ferrocene and ferrocenophane derivatives.
Acknowledgements: The authors would like to acknowledge financial support by the Deutsche
Forschungsgemeinschaft (PI 353/9-1).
References:
[1] R.Sebesta et al., Tetrahedron: Asymmetr. 2006, 17, 2531.
[2] I. Manners, D. Herberg, U.Mayer, Angew. Chem. Int. Ed. 2007, 46, 5060.
[3] P. Jutzi et al., Angew. Chem. 1986, 98, 163.
[4] M. Denk, R. West et al, J. Am. Chem. Soc. 1994, 116 , 2691.
Poster presentation - P057
Formation and Functionalization of Intermetalloid Clusters
Lies Broeckaert (a,b), Florian Weigend, Stefan Mitzinger (1), Robert Wilson, Stefanie
Dehnen*
broeckae@staff.uni-marburg.de
(a) Philipps-Universität Marburg, Fachbereich Chemie and Wissenschaftliches
Zentrum für Materialwissenschaften (WZMW), Hans-Meerwein-Straße, D-35043
Marburg.
(b) Institut für Physikalische Chemie , Karlsruher Institut für Technologie (KIT)
The formation mechanism of intermetalloid clusters is still widely unexplored. In this
work we try to understand the formation processes, by combining new quantum
chemical (DFT) methods and experimental studies (inorganic synthesis,
characterization). The investigations are started from known precursor molecules, but
also include new, unknown cluster structures (reactive intermediates) to make
suggestions for the stepwise formation of two new 12- and 14-atom (Ge/As) cages,
including a tantalum atom, [Ta@Ge8As4]3– and [Ta@Ge8As6]3– (cf. Figure). We make
use of aninorganic retro-synthetic approach.[1] Next, the chemical reactivity of group
14/15 (Ge/As, Sn/Bi, Pb/Bi) clusters is investigated. Quantum chemical calculations
are performed to study the functionalization with different organic ligands. DFT
calculations help to rationalize the synthesis and choose the most promising ligands.
Figure 1. Structures and composition of the 12-atomic [Ta@GeAs](left) and the 14-atomic
[Ta@GeAs]cage (right), embedding Ta.[1a] Ge atoms are colored in yellow and As in blue.
Acknowledgements: This work was supported by the Alexander von Humboldt Stiftung.
References:
[1] (a) S. Mitzinger, L. Broeckaert, W. Massa, F. Weigend, S. Dehnen, Chem. Comm. 2015, 51, 3866;
(b) S. Mitzinger, L. Broeckaert, W. Massa, F. Weigend, S. Dehnen, 2015, submitted.
Poster presentation - P058
Reactivity of M/14/15 Intermetalloid Clusters Toward Organic and
Main Group Organometallic Compounds
Robert Wilson, Stefanie Dehnen*
robert.wilson@chemie.uni-marburg.de
Fachbereich Chemie, Philipps-Universität Marburg
Hans-Meerwein-Straße, D-35032, Marburg
Our group has reported that the binary tetrahedral 14/15 Zintl ions, [Tt2Bi2]2- (Tt = Sn,
Pb), react with transition metal and lanthanide complexes in ethylenediamine to afford
ternary M/14/15 intermetalloid clusters.[1] The geometric and electronic structures of
these unique clusters have been thoroughly analyzed; however, study of their
chemistry is inhibited by poor solubility in (or interaction with) organic non-polar or
polar aprotic solvents. It is known that 9-atom group 14 Zintl ions ([Ge9]4-, [Sn9]4-,
and [Ge9-xSnx]4-) may be functionalized with alkyl, alkenyl, and main group
organometallic moieties, and that addition of external ligands to these compounds can
have a dramatic effect on their reactivity and solubility.[2] With this in mind we have
undertaken a study of the reactivity of [Tt2Bi2]2-, and its derivative intermetalloid
clusters, toward organic and main group organometallic compounds (Figure 1). The
ability of these clusters to undergo functionalization, cation exchange, and their
behavior in alternative solvent systems will be evaluated. Preliminary results of this
study are presented herein.
Figure 1. Examples of 14/15 and M/14/15 clusters, [Sn2Bi2]2- and [Pd3@Sn8Bi6]4-, and
potential main group reactants.
References:
[1] (a) F. Lips, R. Clerac, S. Dehnen, Angew. Chem. Int. Ed. 2011, 50, 960-964; (b) F. Lips, R. Clerac,
S. Dehnen, J. Am. Chem. Soc. 2011, 133, 14168-14171; (c) F. Lips, S. Dehnen, Angew. Chem. Int. Ed.
2011, 50, 955-959; (d) R. Ababei, J. Heine, M. Holynska, G. Thiele, B. Weinert, X. Xie, F. Weigend,
S. Dehnen, Chem. Commun. 2012, 48, 11295-11297; (e) R. Ababei, W. Massa, B. Weinert, P. Pollak,
. ie, R. Clérac , F. Weigend, S. Dehnen, Chem. Eur. J. 2015, 21, 386-394.
[2] (a) M. W. Hull, S. C. Sevov, Inorg. Chem. 2007, 46, 10953-10955; (b) F. Li, S. C. Sevov, J. Am.
Chem. Soc. 2014, 136, 12056-12063.
Poster presentation - P059
An Efficient Approach to Ternary Intermetalloid Clusters and Novel
Zintl Ions
Bastian Weinert, Prof. Dr. Stefanie Dehnen*
weinert4@staff.uni-marburg.de
Fachbereich Chemie der Philipps-Universität Marburg
Hans-Meerwein-Straße D-35043 Marburg
In the past, we exclusively used binary Zintl anions with a combination of Group
14/15 elements as well-soluble precursors, namely [Sn2Sb2]2− and [Sn2Bi2]2−. This has
led to the generation of a large variety of ternary anions such as [Pd3@Sn8Bi6]4–,
[Ln@Sn7Bi7] − and [Ln@Sn4Bi9] − (Ln = La, Ce).[1,2] Our current investigations again
extent this field by transferring our approach to the Group 13/15 element combination
[GaBi3]2− and [InBi3]2−.[3] Here, we present first results of this variation that indicate
the subtle influence of charges, atomic radii and Lewis basicities of the involved
elements. Interestingly with Ln = La, Ce, Nd, we also obtained clusters with novel
structures
or
different
charges,
{[Ln@In2Bi11](µ-Bi)2[Ln@In2Bi11]} −,[4]
[Sm@HGa2Bi11]x3−/[Sm@H3Ga3Bi10]1-x3−.[5] Besides characterization of the
compounds, our studies include formation mechanisms and electronic structures of
the uncommon intermetalloid cages.
Figure 1. Reaction scheme with resulting intermetalloid clusters and Zintl anions.
Acknowledgements: This work was supported by the Deutsche Forschungsgemeinschaft (DFG, GRK
1782) and the Fonds der Chemischen Industrie (FCI, Chemie-Fonds-Stipendium for Bastian Weinert)
References:
[1] F. Lips, R. Clérac, S. Dehnen, J. Am. Chem. Soc. 2011, 133, 14168.
[2] F. ips, M. Hołyńska, R. Clerac, U. inne, I. Schellenberg, R. Pöttgen, F.Weigend, S. Dehnen, J.
Am. Chem. Soc. 2012, 134, 1181.
[3] L. Xu, S. C. Sevov, Inorg. Chem. 2000, 39, 5383.
[4] B. Weinert, F. Weigend, S. Dehnen,* Chem. Eur. J. 2012, 18, 13589.
[5] B. Weinert, F. Müller, K. Harms, S. Dehnen,* Angew. Chem. Int. Ed. 2014, 53, 11979.
Poster presentation - P060
Subsequent chemistry of the Ge9 Zintl anion
Dr. O. Kysliak, Prof. Dr. A. Schnepf*
alexchem1987@gmail.com
Institute of Inorganic Chemistry, University of Tübingen
Auf der Morgenstelle 18, GER-72076, Tübingen
The chemistry of polyhedral Ge9 compounds is of the great interest for cluster and
material chemists. It became especially fruitful during last years [1]. The first silylsubstituted metalloid cluster Ge9R3- (R = -Si(SiMe3)3) was obtained via a cocondensation route as reported by Schnepf in 2003[2]. Since in 2012 Sevov et al.
published a more straightforward synthesis of this compound from K4Ge9 and RCl [3],
direct modifications of Ge9clusters during substitution reaction with different R’
became possible. Here we report on the synthesis of a cluster anion with a modified
silyl ligand [Ge9RPh3]- (RPh = -Si(SiMe3)2(SiPh3)) together with first subsequent
reaction of this compound leading to HgGe18RPh6. Additionally, further investigations
on the reaction procedure led to discovery of coordinately unsaturated metalloid
cluster anion Ge9R22-, which opens the possibility to synthesize a differently
substituted germanium core for the first time.
References:
[1] S. Scharfe, F. Kraus, S. Stegmaier, A. Schier and Th.F. Fässler, Angew. Chem. Int. Ed., 2011, 50,
3630.
[2] A. Schnepf, Angew. Chem. Int. Ed., 2003, 42, 2624.
[3] F. Li, S.C. Sevov, Inorg. Chem., 2012, 51, 2706.
Poster presentation - P061
Synthesis and Reactivity of Novel Amino(imino)metallylenes
Tatsumi Ochiai, Shigeyoshi Inoue
tatsumi.ochiai@campus.tu-berlin.de
Technische Universität Berlin, Institute of Chemistry
Straße des 17. Juni 135, 10623 Berlin
The imidazolin-2-iminato ligand may act as a 2σ- and either a 2π- or a π-electron
donor and the properties of transition-metal complexes of this ligand have been
investigated thoroughly by Tamm and co-workers.[1] Recently, our group has
described an silicon(II) compound stabilized by the imidazolin-2-iminato ligand.[2]
However, research on Group 14 compounds comprising this ligand system has been
neglected in recent years. Herein, we describe the synthesis and reactivity of novel
amino(imino)stannylene
1a
and
germylene
1b.[3]
The
novel
amino(imino)metallylenes 1a, b were prepared by conversion of HNIPr (NIPr =
bis(2,6-diisopropylphenyl)imidazolin-2-imino) with one equiv of Lappert’s reagent
(E[N(SiMe3)2]2, E = Sn, Ge). The reactions of 1a, b with B(C6F5)3 furnishes the borate
salts 2a, b, respectively, though methyl-abstraction and ring-closing reaction.
Treatment of 1a with DMAP (para-dimethylaminopyridine) yields its Lewis base
adduct 3a and the reaction of 1b with Fe2(CO)9 affords iron carbonyl complex 4b.
Furthermore, the reaction of 1a with one equiv of trimethylsilyl azide results in
replacement of the amino group at the tin center by an N3substituent with concomitant
elimination of N(SiMe3)3, to afford dimeric [N3SnNIPr]2 5a.
Figure 1. Reactivity of amino(imino)metallylenes.
References:
[1] X. Wu, M. Tamm, Coord. Chem. Rev. 2014, 260, 116.
[2] S. Inoue, . eszczyńska, Angew. Chem. Int. Ed. 2012, 51, 8589.
[3] T. Ochiai, D. Franz, E. Irran, S. Inoue, Chem. Eur. J. 2015, DOI: 10.1002/chem.201500607.
Poster presentation - P062
Bis(amido)phosphanes and their use as ligands for 14th group metals
Jan Vrana*, Zdenka Ruzickova, Libor Dostal
st20169@student.upce.cz
Department of General and Inorganic Chemistry, University of Pardubice
Studentska 95, CZE-53210, Pardubice
Boramidinates[1] and amidinates[2] were used as suitable ligands for both transition
and main group metals. Analogical compounds, bis(amido)phosphanes, were also
proven to be as useful ligands in organometallic and coordination chemistry[3], but
their chemistry was studied in significantly lower extent. Bis(amido)phosphanes may
have a wide range of bonding properties, since they can act as both monoanionic and
dianionic[4] ligands, where the ligand is bonded by either covalent or coordination
bond
to
the
central
atom.
Novel
germanium(II)
and
tin(II)
bis(organoamido)phosphanes (for example see Figure 1) were prepared.
Characterization of lithium and potassium precursors is also included.
Figure 1. Molecular structure of prepared Germanium(II) compound, hydrogen atom were
omitted for clarity.
Acknowledgements: The authors thank the Grant agency of the Czech Republic project no.
P207/11/0223.
References:
[1] C. Fedorchuk, M. Copsey and T. Chivers, Coord. Chem. Rev., 2007, 251, 897.
[2] (a) F. Edelmann, Adv. Organomet. Chem. 2008, 57, 183; (b) M. Asay, C. Jones and M. Driess;
Chem. Rev. 2011, 111, 354.
[3] B. Eichhorn, H. Noth, T. Seifert, Eur. J. Inorg. Chem., 1999, 21, 2355.
[4] M. C. Copsey, T. Chivers, Dalton Trans., 2006, 4114.
Poster presentation - P063
η3-Allyl Coordination at Tin(II) – Reactivity towards Triplebonds
Kilian M. Krebs, Jessica Wiederkehr and Lars Wesemann*
kilian.krebs@uni-tuebingen.de
Institut für Anorganische Chemie, Universität Tübingen
Auf der Morgenstelle 18, 72076 Tübingen (Germany)
Organotin(IV) allyl species have been known for several decades and are well
established reagents in organic allylation reactions.[1] However, η3-allylic
coordination towards tin is rare. In 2010, Power et al. reported the binding of a
terphenyl substituted tin(II) fragment in η3-fashion towards a cyclooctatetraene
dianion.[2] By switching the oxidation state to SnII in allyl tin compounds we expected
new reactivity and coordination modes since unoccupied binding sites will then be
available at the tin atom. Here we present a Sn II allyl complex, synthesized by
reaction of Power’s triisopropyl substituted terphenyl tin(II) chloride[3] with
(C3H5)MgCl, featuring an η3 coordination mode in the solid state and an uncommon
119
Sn NMR chemical shift.[4] Reaction of the tin allyl compound with an excess of
alkyne or benzonitrile leads to the formation of cyclic compounds as main products
(Figure 1). The alkyne induced formation of a tricyclic core goes along with
dimerization of two tin allyl moieties, formation of a new C-C bond and oxidation of
SnII to SnIV. Reaction with benzonitrile results in a 16 membered ring system by
cleavage of the tin allyl bonds, C-H activation/hydrogen migration and dimerization
of two stannylene units.
Figure 1. η3-allyl SnII complex in reaction with alkynes or benzonitrile. Trip = 2,4,6triisopropylphenyl.
References:
[1] Y. Yamamoto, N. Asao, Chem. Rev. (Washington, DC, U. S.) 1993, 93, 2207-2293.
[2] O. T. Summerscales, X. Wang, P. P. Power, Angew. Chem., Int. Ed. 2010, 49, 4788-4790.
[3] B. E. Eichler, L. Pu, M. Stender, P. P. Power, Polyhedron 2001, 20, 551-556.
[4] K. M. Krebs, J. Wiederkehr, J. Schneider, H. Schubert, K. Eichele, L. Wesemann, Angew. Chem.,
Int. Ed. 2015, early view.
Poster presentation - P064
Reversibility in reactions of cyclic distannenes with terminal alkynes
under ambient conditions
Julia Schneider, Jens Henning and Lars Wesemann*
julia.schneider@uni-tuebingen.de
Institut für Anorganische Chemie, Universität Tübingen
Auf der Morgenstelle 18, 72076 Tübingen, Germany
Cycloaddition reactions of unsaturated molecules represent an important reaction
class in organic chemistry. While thermal [2+2] cycloadditions are mostly symmetry
forbidden for classic organic compounds according to the Woodward-Hoffmann rules,
the heavier group 14 alkene homologues show examples of reactions with alkynes
under ambient conditions.[1] Moreover, the reaction of the stannylene Sn[CH(SiMe3)]2
with a strained alkyne[2] and the reactions of Power’s distannynes with ethylene[3]
show reversibility. Here we present the reactivity of distannenes 1 and 2 towards
terminal alkynes, leading to the formal [2+2] cycloaddition products 3-5.
Interestingly, distannene 1 reacts reversibly at ambient temperature with
trimethylsilylacetylene and phenylacetylene in aromatic solvents, while distannene 2
shows an irreversible reaction with phenylacetylene under the same reaction
conditions (Figure 1). Experimental and computational studies to further investigate
the observed behavior are presented and discussed.
Figure 1. Reaction of distannene 1 and 2 with terminal alkynes (Mes = 2,4,6trimethylphenyl).
References:
[1] a) A. Krebs, A. Jacobsen-Bauer, E. Haupt, M. Veith, V. Huch, Angew. Chem. 1989, 101, 640–642.
b) Weidenbruch, A. Schäfer, H. Kilian, S. Pohl, W. Saak, H. Marsmann, Chem. Ber. 1992, 125, 563–
566. c) V. Y. Lee, T. Fukawa, M. Nakamoto, A. Sekiguchi, B. L. Tumanskii, M. Karni, Y. Apeloig, J.
Am. Chem. Soc. 2006, 128, 11643–11651.
[2] L. R. Sita, R. D. Bickerstaff, J. Am. Chem. Soc. 1988, 110, 5208–5209.
[3] Y. Peng, B. D. Ellis, X. Wang, J. C. Fettinger, P. P. Power, Science 2009, 325, 1668–1670.
Poster presentation - P065
C,N-Chelated Organotin(IV) Azides as Precursors for Substituted
Tetrazoles
Petr Švec,
arel Bartoš, Zdeňka Růžičková, Aleš Růžička
petr.svec2@upce.cz
Department of General and Inorganic Chemistry, University of Pardubice
Studentská 573, CZ-53210, Pardubice, Czech Republic
Last year we described the preparation and structural characterization of two mixed
organotin(IV) amido-azides bearing either C,N-chelating and/or bulky amido
ligands.[1] These species were prepared by the reaction of starting stannylene with
trimethylsilyl azide via the oxidative addition. Meanwhile we have also synthesized
and structurally characterized some other C,N-chelated organotin(IV) azides using the
substitution protocol (i.e. reaction of an organotin(IV) chloride with excess NaN3).
These species may be employed within the click chemistry.[2] Corresponding
tetrazoles are thus formed when mentioned C,N-chelated organotin(IV) azides react
towards various substituted acetonitriles (see Figure). The presentation will discuss
both synthetic details and structural characterization (NMR spectroscopy, XRD
analysis) of prepared tetrazoles bearing triorganotin(IV) moieties.
Figure 1. Reactivity of C,N-chelated organotin(IV) azides towards acetonitrile (R = n-Bu,
Ph).
Acknowledgements: The authors would like to thank the Czech Science Foundation (project
P207/12/0223) for the financial support of this work.
References:
[1] P. Švec, Z. Padělková, M. Alonso, F. De Proft, A. Růžička, Can. J. Chem., 2014, 92, 434.
[2] H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem. Int. Ed., 2001, 40, 2004.
Poster presentation - P066
Preparation and Reactivity of Cationic Germanium(II) and Tin(II)
Donor-Acceptor Complexes
Paul A. Gray*, Brian O. Patrick, and Neil Burford
pagray@uvic.ca
Department of Chemistry, University of Victoria
P.O. Box 3065, Stn. CSC Victoria, BC V8W3V6 Canada
Phosphines and amines represent archetypal ligands in transition metal chemistry, and
their complexes are typically depicted involving a Lewis acid-base interaction. Like
transition metals, many cationic p-block centres, some of which bear lone pairs, can
also act as acceptors to Lewis bases and we have previously shown this to be
especially true for cationic group 15 complexes.1 However, the analogous lone-pair
bearing cations of the group 14 elements have not been comprehensively studied.
Neutral group 14 compounds featuring lone pairs have been shown to react with a
variety of small molecules,2 and the reactivity of the corresponding cations represents
an attractive extension of this chemistry. We now present the results of our
investigation into the synthesis, structure, and characterization of a series of Ge(II)
and Sn(II) cations featuring donor-acceptor interactions with amines and phosphines.
The structural parameters of neutral, mono-, and dicationic complexes, will be
presented, and will be rationalized using computational results. These complexes will
also be compared to other cationic, lone pair-bearing p-block complexes, showing
clear trends across the main group. Additionally, further reactivity of these cations,
including examining their coordination chemistry and reactions with small molecules
will be presented.
References:
(1) A. P. M. Robertson, P. A. Gray, N. Burford, Angew. Chem. Int. Ed., 2014, 53, 6050
(2) J. D. Erickson, J. C. Fettinger, P. P. Power, Inorg. Chem. 2015, 54, 1940.
Poster presentation - P067
Versatile precursors: Organotin(IV) hydrides as building blocks for
low-valent tin chemistry
Christian P. Sindlinger, Lars Wesemann*
christian.sindlinger@uni-tuebingen.de
Institut für Anorganische Chemie, Eberhard Karls Universität
Auf der Morgenstelle 18, GER-72076, Tübingen
Compared to organotin monohydrides the chemistry of organotin di- and trihydrides
has been scarcely investigated. The release of dihydrogen or a synthetic equivalent
from Sn(IV) hydrides offers a clean route toward the generation of the highly reactive
organic tin(II) compounds.[1a,b] We investigated selective dehydrogenations of bulky
substituted organotin di- and trihydrides applying a catalytic (A, Scheme 1) and a
stoichiometric (B) approach to form stannylenes and organotin(II) hydrides.[1c,d]
Depending on the conditions clean access to tin-tin coupling products or a variety of
low-oxidation state tin compounds or their monomeric base-adducts is realized. First
results for the applicability of the concept as well as recent attempts to understand the
dehydrogenation process will be presented. Furthermore, the adducts of Nheterocyclic carbenes to stannylenes and organotin(II) hydrides obtained from
approach B reveal intriguing properties and have been tested on their applicability as
ligands in zero-valent platinum group coordination chemistry. A transfer of the
carbene onto the metal is observed, providing the stannylene in the metal coordination
sphere.[2] Examples for complexes featuring cyclic structural motifs of novel Sn(II)-M
interactions are described.
Figure 1. Catalytic (A) and stoichiometric (B) dehydrogenation approaches on organotin(IV)
hydrides and examples for the reactivity of their deriatives.
Acknowledgements: The Fonds der chemischen Industrie and the Studienstiftung d. dt. Volkes are
gratefully acknowledged
References:
[1] (a) X. Fu, W.P. Neumann, J. Organomet. Chem. 1984, C4. (b) C. P. Sindlinger, L. Wesemann,
Chem.Sci, 2014, 5, 2739; (c) B. E: Eichler, P. P. Power, J. Am. Chem. Soc, 2000, 122, 8785; (d) E.
Rivard et al, J. Am. Chem. Soc, 2007, 129, 16197.
[2] C. P. Sindlinger et al., Angew. Chem. In. Ed., 2015, 54, 4087.
Poster presentation - P068
Carbene-Stabilized P(I) Cations
Justin F. Binder, Ala’aeddeen Swidan, Martin Tang, Jennifer H. Nguyen, Charles
L.B. Macdonald*
binderj@uwindsor.ca
Department of Chemistry and Biochemistry, University of Windsor
401 Sunset Ave., N9B 3P4, Windsor, ON, Canada
The discovery of phosphamethine cyanine dyes was a landmark for main group and
phosphorus chemistry in that they were among the first cases of molecules containing
dicoordinate phosphorus centers and they were the first salts in which P-C π bonding
had been observed at ambient temperature.[1] Our group has developed a reliable and
high-yield new route to this important class of compounds through a more convenient
synthetic pathway: the reaction of carbenes with readily prepared triphosphenium
precursors.[2] This reaction template has already shown success for a variety of
relatively stable carbene types (Figure 1) and the result is a growing library of new
compounds which show promise as functional dyes and as ligands for organometallic
chemistry.[3] Experimental and theoretical approaches to assessing the properties and
reactivities of these electron-rich phosphorus compounds are presented.
Figure 1: Synthesis of carbene-stabilized P(I) salts.
References:
[1] P. Jutzi, Angew. Chem. Int. Ed. Eng., 1975, 14, 232.
[2] B.D. Ellis, C.A. Dyker, A. Decken, C.L.B Macdonald, Chem. Commun., 2005, 1965.
[3] J.F. Binder, A. Swidan, M. Tang, J.H. Nguyen, C.L.B. Macdonald, Chem. Commun., 2015, DOI:
10.1039/C5CC00331H
Poster presentation - P069
The Reactivity of Heavy Group 15 Allyl Analogs
Alexander Hinz, Axel Schulz,* Alexander Villinger
alexander.hinz@uni-rostock.de
Department of Chemistry, University of Rostock
Albert-Einstein-Straße 3a, GER-18059, Rostock
Group 15 analogs of allyl anions, [R–E1E2E3–R]–, are of immanent interest to current
research due to the variability of the bulkiness of both organic substituents and
potential redox activity. Only recently, hetero-dipnicta-diazanes, e.g. cyclic [ClP(µNTer)2AsCl] and [ClSb(µ-NTer)2BiCl] or open-chain [Ter–N(SbCl2)PN–Ter] and
[Ter–NP(Cl)2NN–Ter] were obtained utilizing metathesis reactions of the allylanalogs [Ter–NNN–Ter]–, [Ter–NPN–Ter]–, and [Ter–NSbN–Ter]– (Ter = 2,6dimesitylphenyl) with pnictogen chlorides.[1] The more sophisticated allyl analogs [R–
NPP–R]Li and [R–PAsP–R]Li (Mes* = 2,4,6-tri-tertbutyl-phenyl) are known to be
highly sensitive compounds, their reactivity is only scarcely investigated.[2] To
explore the limits of the salt metathesis route we envisaged the synthesis of a
cyclobutane derivative incorporating four different pnictogens via the [R−NAsP−R] −
anion. This allyl-analog was not accessible with Ter substituents, hence Mes* was
utilized. Computations predicted the biradicaloid long-bond NAsPSb heterocyclus as
more stable compared to the [1.1.0]bicyclic short-bond isomer.
Figure 1. Synthetic approach towards the NPAsSb heterocyclus.
Acknowledgements: Financial support by DFG (SCHU 1170/ 11-1) is gratefully acknowledged.
References:
[1] (a) A. Hinz, A. Schulz, A. Villinger, Angew. Chem. Int. Ed. 2014, 54, 668; (b) A. Hinz, A. Schulz,
A. Villinger, J.-M. Wolter, J. Am. Chem. Soc. 2015, DOI 10.1021/jacs.5b00959.
[2] (a) E. Niecke, B. Kramer, M. Nieger, Organometallics 1991, 10, 10; (b) L. S. H. Dixon, L. K.
Allen, R. J. Less, D. S. Wright, Chem. Commun. 2014, 50, 3007.
Poster presentation - P070
PCO− as a Precursor to Novel P-Containing Heterocycles
Thomas P. Robinson, Jose M. Goicoechea*
Thomas.Robinson@chem.ox.ac.uk
University of Oxford, Oxford
12 Mansfield Rd, Oxford, OX1 3TA, UK
The phosphaethynolate (PCO-) has been shown to react with electronically
unsaturated small organic molecules to yield a variety of P-containing heterocycles.[12]
We now show that the reaction between PCO- and a cyclotrisilene (cSi3(Tip)4)
yields a fully inorganic propellane heterocycle following complete cleavage of the
P≡C bond (Figure 1). This species can be decarbonylated through UV-irradiation to
yield a novel [PSi3(Tip)4]- ring.[3] Other P-containing heterocycles are accessible
through the deprotonation of alkynesubstituted phosphinecarboxamides, which are
derived from the reaction between PCO- and propargylamines. These intramolecular
cyclisations yield either 5- or 6-membered ring systems, which can be selectively
targeted by introducing different substituents onto the propargylphosphinecarboxamide precursor.[4]
Figure 1. Reactivity between PCO− and a cyclotrisilene (Tip = 2, , -triisopropylphenyl).
Acknowledgements: The EPSRC and the University of Oxford for financial support.
References:
[1] A. R. Jupp, J. M. Goicoechea, Angew. Chem. Int. Ed. 2013, 52, 10064
[2] X. Chen, S. Alidori, F. F. Pushmann, G. Samtiso-Quinones, Z. Benkő, Z. i, G. Becker, H.–F.
Grützmacher, H. Grützmacher, Angew. Chem. Int. Ed. 2014, 53, 1641
[3] T. P. Robinson, M. J. Cowley, D. Scheschkewitz, J. M. Goicoechea, Angew. Chem. Int. Ed. 2015,
54, 683
[4] T. P. Robinson, J. M. Goicoechea, Chem. Eur. J. 2015, 21, 5727
Poster presentation - P071
Synthesis and chemical studies of Diaza-phospha-ferrocenophanes
Stefan Weller, Rudolf Pietschnig, László Nyulászi, Dietrich Gudat*
stefan.weller@iac.uni-stuttgart.de
Institute of Inorganic Chemistry, University of Stuttgart
Pfaffenwaldring 55, GER-70569, Stuttgart
Little is known about the synthesis and chemical properties of diaza-phosphaferrocenophanes[1]. In connection with our studies[2] on electron rich
tetraaminodiphosphines[3] we were also interested to see if diaza-phosphaferrocenophanes can be used as building blocks in the synthesis of diphosphines
which can be considered to have some potential for the generation of radicals and the
study of intramolecular electron transfer processes. Here, we present our newest
results. The reaction of substituted diamino-ferrocenes 1 with di- or
trihalogenophosphines give either diazaphospha-[3]ferrocenophanes 2 or
diaminoferrocenyliden-bis-phosphanes 3. Subsequent reductive coupling of such
products allowed us to synthesize aminoferrocenyl-substituted diphosphines 4 or
tetraphosphetanes 5, respectively. The reasons which control the different course of
the reactions, the structures, and some selected reactions of these products, will be
discussed.
Figure 1. Reaction scheme of 1,1'-diaminoferrocene.
References:
[1] B. Wrackmeyer, E. V. Klimkina, W. Milius, Z. Naturforsch., 2009, 64b, 1401; (b) B. Wrackmeyer,
E. V. Klimkina, W. Milius, Z. Anorg. Allg. Chem., 2010, 784.
[2] D. Förster, I. Hartenbach, M. Nieger, D. Gudat, Z. Naturforsch., 2012, 67b, 765; (b) O. Puntigam,
D. Förster, N. A. Giffin, S. Burck, J. Bender, F. Ehret, A. D. Hendsbee, M. Nieger, J. D. Masuda, D.
Gudat, Eur. J. Inorg. Chem., 2013, 2041.
[3] J.-P- Bezombes, P. B. Hitchcock, M. F. Lappert, J. E. Nycz, Dalton Trans, 2004, 499; (b) L.
McInnes, K. Müther, V. Naseri, J. M. Rawson, D. S. Wright, Chem. Commun., 2009, 1691
Poster presentation - P072
Ferrocenylene bridged Oligophosphanes
Stefan Borucki, Rudolf Pietschnig*
stefan.borucki@uni-kassel.de
Institute of Chemistry, University of Kassel, Germany
Heinrich-Plett-Str. 40, GER-34132, Kassel
In pioneering work molecular oligo- and polyphosphanes were intensively studied by
Baudler et al.[1] Electrochemical measurements revealed low oxidation potentials of
these kind of compounds to radical cation species. Especially amino substituted
diphosphanes facilitate the fragmentation reaction.[2] The combination of
oligophosphanes with ferrocene as electron reservoir and redox active backbone, such
as II, should support the cleavage of the electron rich P-P bond and generate
potentially stable and persistent radicals. Down to the present day only a single
triphospha-[3]ferrocenophane[3] is known in literature and their chemistry therefore
remains virtually unexplored. We succeeded in synthesizing precursor I starting from
the readily available Fc’(PHtBu)2. Owing to the presence of several stereo centers in
these molecules, a large number of diastereomers can be expected. Interestingly, the
formation of stereoisomers can be controlled in a certain degree by a combination of
ring and steric constraints.[4] Furthermore, this concept has been extended to other
phosphorus containing [3]ferrocenophanes involving other heteroatoms.
Figure 1. Precursor I und dimer II, which can possibly be oxidized to radical cation species.
Acknowledgements: Financial support by the Deutsche Forschungsgemeinschaft and ERA Chemistry
is gratefully acknowledged (PI 353/8-1).
References:
[1] Selected reviews: (a) M. Baudler, K. Glinka, Chem. Rev., 1993, 93, 1623; (b) Chem. Rev., 1994, 94,
1273.
[2] (a) Review: P.P. Power, Chem. Rev., 2003, 103, 789; (b) M.F. Lappert, J.E. Nycz, Dalton Trans.,
2004, 499.
[3] A.G. Osborne, H.M. Pain, M.B. Hursthouse, M.A. Mazid, J. Organomet. Chem., 1993, 453, 117.
[4] C. Moser, F. Belaj, R. Pietschnig, Chem. Eur. J., 2009, 15, 12589.
Poster presentation - P073
N-Heterocyclic Carbene Phosphinidene and Phosphinidyne Metal
Complexes and their Applications
Adinarayana Doddi, Dirk Bockfeld and Matthias Tamm*
adinarayana.doddi@tu-bs.de
Institute of Inorganic and Analytical Chemistry, Technical University Braunschweig
Hagenring 30, 38106 Braunschweig, Germany
Phosphinidenes (R‒P, analogs of carbenes and nitrenes) are a fascinating class of
highly reactive low-valent main-group compounds. They possess unique bonding,
reactivity and structural diversity.[1] Therefore, the electronic tuning of such
phosphorus reagents using different ancillary ligands is an intriguing and challenging
not only from synthetic point of view but also understanding of their chemical
properties. Transition (and also main-group metal) complexes of such novel ligands
could display applications in the small molecule activation as well as in homogeneous
catalysis. Recently, our group has developed a novel method for isolation of an Nheterocyclic carbene supported novel phosphinidene (IPr=P‒SiMe3) (Figure 1) and it
was introduced as a synthon for the preparation of terminal carbene–phosphinidyne
transition metal complexes of the type [(IPr=P)ML n ] (ML n =(η6-p-cymene)RuCl and
(η5-C5Me5)RhCl) (i.e, Figure 1). Their spectroscopic and structural characteristics
show their similarity with arylphosphinidene complexes.[2] The formally mono
negative “IPr=P” ligand is also capable of bridging two or three metal atoms as
demonstrated by the preparation of bi- and trimetallic RuAu, RhAu, Rh2, and Rh2Au
complexes.[3a] Furthermore, several homo and bi metallic coinage metal complexes of
carbene-phosphinidene adduct were isolated.[3b] The newly synthesized cationic dual
gold complexes were found highly active homogeneous catalysts and highlights the
use of carbene-phosphinidenes as supporting ligands. In this presentation, syntheses,
bonding and applications of this new class of formally phosphorus (I) reagents will be
discussed.
Figure 1. Synthesis of a carbene-phosphinidyne transition metal complex.[3a]
References:
[1] (a) O. Back, M. H. Ellinger, C. D. Martin, D. Martin, G. Bertrand, Angew. Chem. Int. Ed. 2013, 52,
2939–2943. (b) G. Frison, A. Sevin, J. Organomet. Chem, 2002, 643–644, 105-111.
[2] H. Aktaş, J. C. Slootweg, . ammertsma, Angew. Chem. Int. Ed. 2010, 49, 2102-2113.
[3] (a) A. Doddi, D. Bockfeld, T. Bannenberg, P. G. Jones, M. Tamm, Angew. Chem. Int. Ed. 2014,
53, 13568 –13572. (b) A. Doddi, D. Bockfeld, A. Nasr and M. Tamm, manuscript in preparation.
Poster presentation - P074
NEW SYNTHETIC APPROACH TO THE SYNTHESIS OF NHCPHOSPHINIDENE COMPOUNDS
Otfried Lemp, Carsten von Hänisch
Lemp@students.uni-marburg.de
Department of Chemistry, Philipps-Universität Marburg
Hans-Meerwein-Straße 4 35032 Marburg
Recently, the N-heterocyclic-carbene stabilized parent phosphinidene (PH) was
isolated and fully characterized.[1] We present a new synthetic approach to generating
such compounds via oxidation of LiPH2with NHC transition metal halides and further
reactions of these species, specially with [W(CO)5(thf)]
Figure 1. Crystal Structure of IMes:PHW(CO)5
References:
[1] (a) Hansen K..; Szilvási T.; Blom B.; Irran E.; Driess M. Chemistry Eur. J., 2014, 20, 1947.
(b) Doddi A.; Bockfeld D.; Bannenberg T.; Jones P. G.; Tamm M. Angew. Chem ,2014, 126, 13789.
(c) Tondreau A. M.; Benko Z.; Harmer J. R.; Grützmacher H. Chem. Sci., 2014, 5, 1545.
Poster presentation - P075
Zwitterionic Triphospheniums as Multidentate Donors
Stephanie C. Kosnik, G. J. Farrar, C.L.B. Macdonald*
kosniks@uwindsor.ca
Department of Chemistry and Biochemistry
University of Windsor, 401 Sunset Ave, Windsor, On Canada
Triphosphenium cations have a diverse and fruitful history originating from the
seminal work of Schmidpeter in the 1980’s.[1] Despite their stability, there are few
reports of coordination chemistry involving these compounds, which is most likely a
consequence of the presence of reactive anions and perhaps the positive charge on the
potential donor.[2] In order to circumvent these issues, we have been interested in the
generation of neutral triphosphenium species[3], as it has recently been shown that
such neutral species do in fact increase the donating ability of the P1 center.[4,5]
Furthermore, the use of an anionic backbone could serve as an alternative donor site,
thus increasing the potential utility of these molecules as multidentate donors. The
investigations presented herein include: the characterization of complexes with
various transition metals and structural assessment of many of these molecules via Xray crystallography.
References:
[1] A. Schmidpeter, S. Lochschmidt, W. S. Sheldrick, Angew. Chem. Int. Ed. Engl. 1982, 21, 63–64.
[2] B. D. Ellis, C. L. B. Macdonald, Coord. Chem. Rev. 2007, 251, 936–973.
[3] S. C. Kosnik, G. J. Farrar, E. L. Norton, B. F. T. Cooper, B. D. Ellis, C. L. B. Macdonald, Inorg.
Chem. 2014, 11, 13061–13069.
[4] J. W. Dube, C. L. B. Macdonald, P. J. Ragogna, Angew. Chem. Int. Ed. Engl. 2012, 51, 13026–30.
[5] J. W. Dube, C. L. B. Macdonald, B. D. Ellis, P. J. Ragogna, Inorg. Chem. 2013, 52, 11438–49.
Poster presentation - P076
Synthesis and Photophysical Properties of Novel PhosphorusContaining Conjugated Systems
Alicia López-Andarias, Philip Hindenberg, Carlos Romero-Nieto*
alicia.lopez.andarias@oci.uni-heidelberg.de
Organisch-Chemisches Institut, University of Heidelberg
Im Neuenheimer Feld 270, Room 270, GER-69120, Heidelberg
In the last decades, the design and development of novel multifunctional materials
based on heterocyclic compounds has become an important research topic. The
introduction of heteroatoms into π-conjugated molecules enables modulating the
HOMO and LUMO energy levels and thus tailoring the optoelectronic properties. In
this context, phosphorus heterocycles offer unique means to keep control over the
photophysics of π-conjugated materials. As a matter of fact, orbital interactions
between the phosphorus centers and the π-system give rise to a low-lying LUMO and,
therefore, to an acceptor character.[1] Moreover, phosphorus atoms provide selective
centers for reversible post-functionalization reactions with transition metals, Lewis
acids, oxidizing and alkylating agents.[2] Recently, phosphorus-based systems have
emerged as promising luminescent materials with outstanding properties.[1] This
chemistry is, however, at its early stage; exploring the full potential of phosphorus
heterocycles requires certainly the development of new architectures. In this
communication, we will present the synthesis and properties of novel, fused
phosphorus-containing systems. We will report a detailed study on the photoelectrochemical features of our new phosphorus-based heterocycles. Moreover, we
will discuss the impact of extending the π-conjugation through different
heteroaromatics into the optoelectronic properties.
Acknowledgements: Financial support by the Fonds der Chemischen Industrie, Germany, is gratefully
acknowledged. We also thank the Organisch-Chemisches Institut, Universität Heidelberg, Germany,
for its support.
References:
[1] T. Baumgartner, Acc. Chem. Res., 2014, 47, 1613-1622.
[2] Y. Matano, A. Saito, T. Fukushima, Y. Tokudome, F. Suzuki, D. Sakamaki, H. Ito, K. Tanaka, H.
Imahori, Angew. Chem. Int. Ed., 2011, 50, 8016-8020.
Poster presentation - P077
Cycloaddition of P–C Single Bonds? The Case of Oxaphosphirane
Complexes and ortho-Benzochinones
Payal Malik,(a) Arturo Espinosa,* (b) Gregor Schnakenburg, (a) and Rainer
Streubel*(a)
r.streubel@uni-bonn.de
(a) Institut für Anorganische Chemie der Rheinischen Friedrich-WilhelmsUniversität Bonn, Gerhardt-Domagk-Strasse 1, 53121 Bonn (Germany)
(b) epartamento de u mica rgánica, acultad de u mica, Universidad de
Murcia, Campus de Espinardo, 30100, Spain
Due to their P=C double bond, phosphaalkenes have been used as versatile building
blocks in organic synthesis,[1] catalysis[2] and polymer[3] chemistry; one example is
their [4+2] cycloaddition with ortho-benzochinones. The latter are also known to react
with tertiary phosphanes in [4+1] cycloaddition reactions due to the P-lone pair.[4] In
contrast, P–C single bonds are known to be inert towards cycloaddition reactions. To
address the quest of P–C single bond reactivity towards cycloaddition reactions,
investigations were launched, recently, focusing on endocyclic P–C bonds of
heterocyclic ligands. Herein, reactions of oxaphosphirane complexes with tetrachloro
ortho-benzochi-none are reported together with DFT calculations of reaction pathway
dependencies on redox potentials. The obtained 1,3,6,2-trioxaphospha-heptane
complexes 1–3 were fully characterized by IR, 1H, 13C, 31P NMR and single crystal
X-ray diffraction techniques.[5]
Scheme 1. Reactions of oxaphosphirane complexes with tetrachloro ortho-benzochinone.
Acknowledgements: This work was financially supported by the Deutsche Forschungsgemeinschaft
(SFB 13 “Chemistry at Spin Centers”).
References:
[1] (a) F. Mathey, Chem. Rev.,1990, 90, 997–1025; (b) M. Regitz, Chem. Rev., 1990, 90, 191–213.
[2] P. L. Floch, Coord. Chem. Rev.,2006, 250, 627–681.
[3] J. I. Bates, J. Dugal-Tessier, D. P. Gates, Dalton Trans., 2010, 39, 3151–3159.
[4] (a) T. Gust, W.-W. du Mont, R. Schmutzler, C. G. Hrib, C. Wismach, P. G. Jones, Phoshorus,
Sulfur. Silicon Relat. Elem., 2009, 184, 1599–1611; (b) L. Weber, Eur. J. Inorg. Chem., 2000, 2425–
2441.
[5] P. Malik, G. Schnakenburg, A. Espinosa, R. Streubel, submitted.
Poster presentation - P078
Reactions of the Pentelidene Complexes [Cp*E{W(CO)5}2]
(E = P, As) with Heterocumulenes
Michael Seidl, Manfred Scheer*
Michael1.Seidl@chemie.uni-regensburg.de
Institute of Inorganic Chemistry, University of Regensburg
Universitätsstraße 31, GER-93053, Regensburg
Phosphinidenes (R–P) are low-valent organophosphorus compounds containing 6
valence electrons which are unstable as ‘free’ molecules. They can be stabilized on
transition-metal fragments by various ways. Our research interest is dedicated to
bridging
pentelidene
complexes
of
the
type
[Cp*E{W(CO)5}2]
(E = P, As; Cp* = C5Me5) due to their high diversity in reactivity. These complexes
show interesting reaction behavior under thermolytic[1] and photolytic[2] conditions.
They also reveal high reactivity towards nucleophiles like isonitriles.[3] The reactivity
of the pentelidene complexes towards heterocumulenes, like cabodiimides,
alkylazides and carboimidophosphenes will be presented. The carbodiimides and the
alkylazides react with the pentelidene complexes by a 1,3-cycloaddition to form novel
four membered heterocycles like the triazaphosphete complexes.[4] The reaction with
the carboimidophosphene leads not to such heterocycles, however the first example of
a 1,3-butadiene analog is obtained consisting only of mixed heavier Group 15
elements.
Figure 1. Reactions of the pentelidene complexes with heterocumulenes.
Acknowledgements: Deutsche Forschungsgemeinschaft (DFG).
References:
[1] M. Scheer, E. Leiner, P. Kramkowski, M. Schiffer, G. Baum, Chem. Eur. J. 1998, 4, 1917-1923.
[2] M. Scheer, C. Kuntz, M. Stubenhofer, et al, Angew. Chem. Int. Ed. 2009, 48, 2600-2604.
[3] M. Seidl, M. Schiffer, M. Bodensteiner, A. Y. Timoshkin, M. Scheer, Chem. Eur. J. 2013, 19,
13783-13791.
[4] M. Seidl, C. Kuntz, M. Bodensteiner, A. Y. Timoshkin, M. Scheer, Angew. Chem. Int. Ed. 2015,
54, 2771-2775.
Poster presentation - P079
1,3,2-Dioxaphosphol-4-enes: synthesis of a novel inorganic ring
system
Philip Junker, Vitaly Nesterov, Rainer Streubel
s6phjunk@uni-bonn.de
Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität
Bonn
Gerhard-Domagk-Str. 1, GER-53121 Bonn
The first synthesis of a σ4λ5-oxaphosphirane was described by Röschenthaler in
1978,[1] whereas σ3λ3-oxaphosphiranes still remain unknown. In contrast, their
transition metal(0) complexes, first reported by Mathey in 1990, have been
synthesized via epoxidation of phosphaalkene complexes,[2] or via phosphinidene
complex transfer reaction onto aldehydes as described by Streubel et al.[3] But a
broader investigation was hampered until the advent of new protocol: the reaction of
Li/Cl phosphinidenoid complexes 2 and carbonyls at low temperature, which was
reported in 2007 by Streubel et al.[4] Since then a wealth of new structures were
established departing from oxaphosphirane complexes, including the first C-acyloxaphosphirane complex 3[5] obtained via reaction of 2 with a α,β-diketone (Scheme).
While a derivative of 3 was obtained in good yields, complex 4 having a novel 1,3,2dioxaphosphol-4-ene ligand was obtained as by-product, only, and the pathway could
not be clarified. Herein, detailed investigation on syntheses of novel C-acylsubstituted oxaphosphirane and 1,3,2-dioxaphospholene complexes 3,4 will be
presented, including a facile protocol for 4.
Acknowledgements: This work was financially supported by the DFG (STR 411/26-3 and 411/29-1),
and it is dedicated to Prof. F. Mathey
References:
[1] G. V. Röschenthaler, K. Sauerbrey, R. Schmutzler Chem. Ber. 1978, 111, 3105.
[2] S. Bauer, A. Marinetti, L. Ricard, F. Mathey, Angew. Chem. Int. Ed. Engl. 1990, 29, 1166.
[3] R. Streubel, A. Kusenberg, J. Jeske, P. G. Jones, Angew. Chem. Int. Ed. Engl. 1994, 33, 2427.
[4] a) A. Özbolat, G. von Frantzius, M. Nieger, R. Streubel, Angew. Chem. Int. Ed. Engl. 2007, 46,
9327; b) R. Streubel, M. Bode, J. M. Pérez, G. Schnakenburg, J. Daniels, M. Nieger, P. G. Jones, Z.
Anorg. Allg. Chem. 2009, 635, 1163; c) M. Bode, J. Daniels, R. Streubel, Organometallics 2009, 28,
4636.
[5] L. Abdrakhmanova, G. Schnakenburg, A. Espinosa, R. Streubel, Eur. J. Inorg. Chem. 2013,1727.
[6] V. Nesterov, P. Junker, G. Schnakenburg, R. Streubel, manuscript in preparation.
Poster presentation - P080
Synthesis of asymmetric phosphorus diiminopydrine complexes
Siu Kwan Lo and Jose M Goicoechea*
siu-kwan.lo@chem.ox.ac.uk
Department of Chemistry, Chemistry Research Laboratory, University of Oxford
12 Mansfield Rd, Oxford, OX1 3TA, UK
The development of geometry-constrained catalysts using pincer ligand scaffolds has
received significant attention in the field of organometallic chemistry. However
species in which such ligands are used in the immediate coordination sphere of
maingroup elements, such as phosphorus, are much rarer. Three-coordinate
complexes of phosphorus(III) generally exhibit trigonal monopyramidal geometries
due to the presence of a stereochemical lone pair (minimizing interelectronic
repulsion according to VSEPR theory). Constrains such systems in ‘T-shaped’
geometries by using planar pincer ligands can be used as a strategy to access
molecules with two orthogonal orbitals (one filled: lone pair; one empty: typically
stabilized via π-interactions) which in principle should allow for the heterolytic
cleavage of small molecule substrates.[1] We have recently observed that reaction of
PCl3 with an α,α’-diiminopyridine ligand (L) in dichloromethane results in clean
formation of the phosphorus-centered complex [1][Cl] (see Scheme 1). This
observation is in contrast with previously reported observations on the reactivity of
other phosphorus(III) halides with L.[2] Activation of one of the C–H bonds of an
imino methyl group and subsequent reduction of the other imine group in the α,α’diiminopyridine has been observed. 1 has been studied extensively by X-ray
crystallography, 1H and 31P NMR spectroscopy. Reactivity studies on this product,
and other related main-group systems, are currently on-going.
Scheme 1
Acknowledgements: We thank the University of Oxford for financial support of this research.
References:
[1] (a) N. L. Dunn, A. T. Radosevich, J. Am. Chem. Soc. 2012, 134, 11330. (b) S. M. McCarthy, Y.-C
Lin, D. Devarajan, J. W. Chang, H. P. Yennaway, R. M. Rioux, D. H. Ess, A. T. Radosevich, J. Am.
Chem. Soc. 2014, 136, 4640.
[2] C. D. Martin, P. J. Ragogna, Dalton Trans., 2011, 40, 11976.
Poster presentation - P081
Synthesis, thermolysis and photochemistry of oxaphosphirane
complexes
Melina Klein, Rainer Streubel*
melinaklein@uni-bonn.de
Institut für Anorganische Chemie, Rheinischen-Friedrich-Wilhelms-Universität Bonn
Gerhard-Domagk-Str. 1, GER-53121 Bonn
Oxaphosphirane complexes are known since the nineties but a broad development of
the chemistry was hampered by low yield methodologies.[1] This changed recently as
a new facile protocol was reported,[2] enabling the systematic study of a broad range
of oxa-phosphirane complexes, obtained under mild conditions and with high
diastereoselectivity. Herein, we describe synthesis of oxaphosphirane complexes
bearing donor substituents[3] at the ring carbon atom as well as investigations on their
thermolysis and photochemistry. For example, a thermal ring‑expansion of 2 was
discovered leading to the new chelate complexes 3 (route A) and irradiation to
complexes 4 representing a dimer‑like product (route B).[4] Preliminary investigations
on reactions of 1 with NHC 5 (route C) revealed formation of complexes 6, which
were used to establish a novel pathway to oxaphosphirane complexes 2.
Acknowledgements: We are grateful to the SFB 13 „Chemistry at Spin Centers“, the DFG (STR
411/29-1) and the DAAD (PPP with Canada/stay of M.K.) for financial support.
References:
[1] (a) S. Bauer, A. Marinetti, L. Ricard, F. Mathey, Angew. Chem. Int. Ed. Engl. 1990, 29, 1166–
1167; (b) R. Streubel, A. Kusenberg, J. Jeske, P. G. Jones, Angew. Chem. Int. Ed. Engl. 1994, 33,
2427–2428;
[2] (a) A. Özbolat, G. von Frantzius, J. M. Pérez, M. Nieger, R. Streubel, Angew. Chem. Int. Ed. Engl.
2007, 46, 9327–9330; (b) M. Bode, J. Daniels, R. Streubel, Organometallics 2009, 28, 4636–4638; (c)
R. Streubel, M. Bode, J. Marinas Pérez, G. Schnakenburg, J. Daniels, M. Nieger, P. G. Jones, Z. anorg.
allg. Chem. 2009, 635, 1163–1171; (d) C. Albrecht, M. Bode, J. M. Pérez, J. Daniels, G.
Schnakenburg, R. Streubel, Dalton Trans. 2011, 40, 2654–2665;
[3] (a) R. Streubel, M. Klein, G. Schnakenburg, Organometallics 2012, 31, 4711–4715; (b) M. Klein,
C. Albrecht, G. Schnakenburg, R. Streubel, Organometallics 2013, 32, 4938–4943;
[4] M. Klein, G. Schnakenburg, R. Streubel, to be published.
Poster presentation - P082
Fluorinated oxaphosphirane complexes: synthesis, redox potentials
and novel reactions
C. Murcia García, A. Espinosa Ferao, A. Frontera and R. Streubel*
murcia@uni-bonn.de
Inorganic Chemistry, University of Bonn
Gerhard-Domagk-Str. 1, GER-53121 Bonn.
Facile access to oxaphosphirane complexes was achieved, recently, using the broadly
applicable synthetic protocol based on the reaction of Li/Cl phosphinidenoid complexes 1 with carbonyl derivatives.[1,2] The interest of tuning the reactivity of oxaphosphirane complexes prompted us to synthesize new derivatives bearing electronwithdrawing groups at carbon, in combination with a potential leaving group with the
required bulkiness at phosphorus, i.e. the triphenylmethyl group.[3] Herein, synthesis
of fluorinated derivatives 2a-d [4] their acid induced ring-expansion reaction to give 4
[5,6]
as well as an unexpected outcome (3) of the reaction between complex 1
(M = Mo) and benzophenone[7] are presented. Preliminary experiments aiming at
transient complexes 5a-d via reductive SET reactions as well as theoretical
calculations and results of cyclic voltammetry measurements will be discussed.
Figure 1. Synthesis and reactions of fluorinated oxaphosphirane complexes
References:
[1] a) A. Özbolat, G. von Frantzius, J. M. Pérez, M. Nieger, R. Streubel, Angew. Chem. Int. Ed. 2007,
46, 9327-9330; b) R. Streubel, A. Özbolat-Schön, G. v. Frantzius, H. Lee, G. Schnakenburg, D. Gudat,
Inorg. Chem. 2013, 52, 3313-3325.
[2] V. Nesterov, G. Schnakenburg, A. Espinosa, R. Streubel, Inorg. Chem. 2012, 53, 12343-12349.
[3] C. Murcia García, A. Bauzá, G. Schnakenburg, A. Frontera, R. Streubel, Cryst. Eng. Com. 2015,
17, 1769-1772.
[4] A. Espinosa, R. Streubel, Chem. Eur. J. 2012, 18, 13405-13411.
[5] J. M. Pérez, H. Helten, G. Schnakenburg, R. Streubel, Chem. Asian J. 2011, 6, 1539–1545.
[6] C. Murcia García, R. Streubel, manuscript in preparation.
[7] C. Murcia García, A. Espinosa Ferao, R. Streubel, manuscript in preparation.
Poster presentation - P083
Bimetallic 1,3 Diphosphacyclobutadiene Sandwich Compounds
Christian Rödl and Robert Wolf*
christian.roedl@ur.de
Institute of Inorganic Chemistry, University of Regensburg
Universitätsstraße 31, D-93040, Regensburg
Bis(1,3-diphosphacyclobutadiene) sandwich complexes of type [Co(η4-P2C2R2)2]− are
readily prepared by reacting phosphaalkynes with the cobalt(-I) complex
[Co(anthracene)2]−.[1] Their ability to coordinate further metal atoms through the
phosphorus lone pairs potentially gives access to new oligonuclear complexes and
supramolecular coordination compounds.[2,3] Recently, we reported the preparation of
a series of copper(I), silver(I) and gold(I) complexes of our [Co(η4-P2C2R2)2]− anions.
The resulting bimetallic compounds feature distinct structures that range from simple
molecular 1:1 complexes to coordination polymers and supramolecular assemblies,
e.g. the molecular square [Au{Co(P2C2tBu2)2}]4.[3] Here, we present an extension of
these studies to group 9 and 10 metals. The new dinuclear complexes [(η4C4Me4)Co(CO)2{Co(η4-P2C2tBu2)2}] (1) and [CpNi(PPh3){Co(η4-P2C2tBu2)2}] (2)
have been synthesized by transmetalation of [Tl(thf)2{Co(P2C2tBu2)2}] with
[(C4Me4)Co(CO)2I] and [CpNiBr(PPh3)]. Compounds 1 and 2 have been
characterized by single-crystal X-ray diffraction and spectroscopic techniques. The
cyclic voltammograms of 1 and 2 feature similar reversible redox waves at
E1/2 = −0.1 V for 1 and E1/2 = −0.1 V for 2 (vs. Fc/Fc+ in THF/TBAH). The
experimental results are supported by DFT calculations which give additional insight
into the electronic structures of the investigated complexes.
Figure 1. Synthesis of the new dinuclear complexes 1 and 2.
References:
[1] a) R. Wolf, A. W. Ehlers, J. C. Slootweg, M. Lutz, D. Gudat, M. Hunger, A. L. Spek, K.
Lammertsma, Angew. Chem. Int. Ed. 2008, 47, 4584–4587; Angew. Chem. Int. Ed. 2009, 48, 3104–
3107; b) R. Wolf, A. W. Ehlers, M. M. Khusniyarov, F. Hartl, B. de Bruin, G. J. Long, F. Grandjean, F.
M. Schappacher, R. Pöttgen, J. C. Slootweg, M. Lutz, A. L. Spek, K. Lammertsma, Chem. Eur. J.
2010, 16, 14322–14334.
[2] review on diphosphacyclobutadiene complexes: A. Chirila, R. Wolf, J. C. Slootweg, K.
Lammertsma, Coord. Chem. Rev. 2014, 270, 57–74.
[3] a) J. Malberg, T. Wiegand, H. Eckert, M. Bodensteiner, R. Wolf, Chem. Eur. J. 2013, 19, 2356–
2369; Eur. J. Inorg. Chem. 2014, 1638–1651; c) J. Malberg, M. Bodensteiner, D. Paul, T. Wiegand, H.
Eckert, R. Wolf, Angew. Chem. Int. Ed. 2014, 53, 2771–2775.
Poster presentation - P084
Oxidation and Isomerization of 1,3-Diphosphete Complexes
Eva-Maria Rummel, Manfred Scheer*
eva-maria.rummel@ur.de
Institute of Inorganic Chemistry, University of Regensburg
Universitätsstraße 31, GER-93040 Regensburg
Although 1,3-diphosphacyclobutadiene (1,3-diphosphete) complexes have first been
isolated as early as 1986 by the Nixon and Regitz groups simultaneously,[1] these kind
of complexes are still of interest regarding their coordination behaviour, as current
literature shows.[2] However, as calculations show, the 1,2-diphosphete isomer should
always be the thermodynamically and kinetically favourable isomer.[3]
This work shows the 1,3-diphosphete complexes [(CpꞌꞌꞌCo)n(η4-C2P2R2)] (n = 1: R =
tBu (1), iPr (2); n = 2: R= Me (3)) being reacted with Ag[Al{OC(CF3)}4] (= Ag(pftb))
to form either oxidized species [(CpꞌꞌꞌCo)2(η4-C2P2Me2)]+[pftb]- (4) or isomerize to
form novel 1,2-diphosphete coordination complexes of silver(I): ([{(CpꞌꞌꞌCo)(η4C2P2R2)}nAg2]2+·2[pftb]- (n = 4, R = tBu (5), n = 2, R = iPr (6)).
Figure 1. Isomerization of 1 in the presence of Ag+ to form the 1,2-diphosphete coordination
complex 5.
References:
[1] a) P. Binger, R. Milczarek, R. Mynott, M. Regitz, W. Rösch, Angew. Chem. Int. Ed., 1986, 25, 644;
Angew. Chem., 1986, 98, 645, b) P. B. Hitchcock, M. J. Maah, J. F. Nixon, Chem. Commun., 1986,
737.
[2] a) E.-M. Rummel, M. Eckhardt, M. Bodensteiner, E. V. Peresypkina, W. Kremer, C. Gröger, M.
Scheer, Eur. J. Inorg. Chem., 2014, 1625. b) J. Malberg, T. Wiegand, H. Eckert, M. Bodensteiner, R.
Wolf, Eur. J. Inorg. Chem., 2014, 1638.
[3] S. Creve, M. T. Nguyen and L. G. Vanquickenborne, Eur. J. Inorg. Chem., 1999, 1281.
Poster presentation - P085
Structural Properties of Paraben Substituted Fluorenylidene-Double
Bridged Cyclophosphazenes
Elif Şenkuytu and Gönül enilmez Çiftçi
senkuytu@gtu.edu.tr
Department of Chemistry, Gebze Technical University
Gebze 41400, Kocaeli, Turkey
Phosphazenes are important family of inorganic systems consist of the repeating units
– [N=PR2] – with trivalent nitrogen and pentavalent phosphorus atoms. When the side
group “R” is a halogen, it can be replaced with different groups via nucleophilic
substitution reactions thus forming phosphazene compounds bearing different
properties.[1] Cyclotriphosphazenes could form a core to synthesize a variety of
compounds that can be utilized used as biomedical materials, anticancer and
antimicrobial agents, liquid crystals and organic light emitting diodes.[2] In the current
study, novel cyclotriphosphazene compounds were synthesized and fully
characterized by mass spectrometry, 1H and 31P NMR spectroscopies and elemental
analysis.
Figure 1. Paraben substituted fluorenylidene-double bridged cyclophosphazenes
Acknowledgements: The authors thank to the Scientific and Technical Research Council of Turkey
(TÜBİTA ) for financial support (Project No: 11 Z 1).
References:
[1] (a) V. Chandrasekhar, M. D. Pandey, B. Das, B. Mahanti, K. Gopal, R. Azhakar, Tetrahedron,
2011, 67, 913 (b) G. enilmez Çiftçi, E. Şenkuytu, E. Tanr verdi Eçik, A.
l ç, F. uksel,
Polyhedron, 2011, 30, 2227.
[2] (a) T. ld r m, . Bilgin, G. enilmez Çiftçi, E. Tanr verdi Eçik, E. Şenkuytu, . Uludağ, .
Tomak, A. l ç, Eur. J. Med. Chem, 2012, 52, 213. (b) enilmez Çiftçi, E. Şenkuytu, M. Durmus, F.
uksel, A. l c, Dalton Trans, 2013, 42, 14916.
Poster presentation - P086
The synthesis and characterization of spiro bridged
cyclophosphazene compounds containing two chiral centers
Serap Beşli(a) , Ceylan Mutlu,(a) Fatma Yuksel,(a) Christopher W. Allen(b)
besli@gtu.edu.tr
(a) Department of Chemistry, Gebze Technical University, Gebze-Kocaeli, TURKEY
(b) Department of Chemistry, University of Vermont, Vermont 05405-0125, USA
N,N-spiro bridged octachlorobiscyclotriphosphazene (1) is a new precursor for the
preparation of novel phosphazene derivatives. It is a rigid and stable compound with
four PCl2 groups at the corners of two fused cyclophosphazene rings [1,2]. In this study,
1 was reacted with the di-functional reagent, 3-amino-1-propanol, and the chiral
compounds (2a, 2b, 3a, 3b) containing two equivalent chiral centres were obtained
(Figure 1). All compounds were characterized by elemental analysis, mass
spectrometry, 1H and 31P NMR spectroscopy. The stereogenic properties of
compounds were investigated by chiral HPLC and 31P NMR spectroscopy in the
presence of a chiral solvating agent (CSA).
Figure 1. The reactions of compound 1 with the 3-amino-1-propanol
Acknowledgements: The authors would like to thank the Scientific and Technical Research Council of
Turkey for financial support (Grant 113Z304).
References:
[1] S. Beşli, S. J. Coles, D. B. Davies, A.O. Erkovan, M. B. Hursthouse, A. l ç, Inorg. Chem., 2008,
47, 5042-5044.
[2] S. Beşli, S. J. Coles, D. B. Davies, A. l ç, R. A Shaw, Dalton Trans., 2011, 40, 5307-5315.
Poster presentation - P087
Syntheses, structural characterizations of new phosphazenes bearing
vanillinato and pendant monoferrocenyl groups
asemin Tümer , Nuran Asmafiliz, Zeynel
lç
yasemintumer@karabuk.edu.tr
Department of Chemistry, Karabük University
Department of Chemistry, Karabük University 78050 Karabük, Turkey
Cyclotriphosphazene (N3P3Cl6) is a versatile starting compound for the syntheses of
cyclotriphosphazene derivatives, polyorganophosphazenes and dendrimers.
Cyclotriphosphazene derivatives with different side groups such as alcohols and
amines are attracting increased interest in various areas of technological and
medicinal importance.[1] In this study, the gradual Cl replacement reactions of NN
spirocyclic monoferrocenyl cyclotriphosphazenes (1-3) with the potassium salt of 4hydroxy-3-methoxybenzaldehyde (potassium vanillinate) resulted in the mono (1a–
3a), geminal (gem-1b–3b), non-geminal (trans-1b–3b), tri (1c and 3c) and tetra (1d–
3d) vanillinato-substituted phosphazenes (Scheme 1). All the phosphazene derivatives
have stereogenic P-center(s), except tetra-substituted ones. The structures of the new
phosphazene compounds were determined by FTIR, MS, 1H-, 13C- and 31P-NMR
spectral data.[2]
Scheme 1 The phosphazene derivatives obtained from the reactions of tetrachloro
monoferrocenylphosphazenes with potassium vanillinate.
Acknowledgements: The authors acknowledge the “Scientific and Technical Research Council of
Turkey” Grant No.112T0 3.
References:
[1] Gleria M, Jaeger De, Applicative Aspect of Cyclophosphazenes. Nova Science Publishers, New
York, 2004.
[2]. . Tümer, . . oc, N. Asmafiliz, Z. l c, T. Hökelek, H. Soltanzade, . Ac k, M. . ola, A.
O. Solak, J Biol Inorg Chem, 2015, 20, 165–178.
Poster presentation - P088
The substitution reactions of a mono ansa
fluorodioxycyclotriphosphazene derivative with diols
Ceylan Mutlu , Serap Beşli, Fatma uksel
ceylanmutlu@gtu.edu.tr
Department of Chemistry
Gebze Technical University, Gebze-Kocaeli, TURKEY
Nucleophilic substitution reactions are of central in cyclophosphazene chemistry due
to the complexity and variability of the reaction mechanisms and the broad range of
regio- and stereo- chemical outcomes of these reactions.[1-3] In this work, the reactions
of N3P3Cl4[OCH2(CF2)3CH2O] (1) with the disodium salts of 1,3-propandiol and
tetraethyleneglycol were investigated in order to determine the reaction pathways and
mechanism of nucleophilic substitution at the PCl2 and PCl(OR) phosphorus atoms.
The products were characterized by elemental analysis, mass spectrometry, 1H and 31P
NMR spectroscopy and X-ray crystallography. The reactions of compound 1 with
disodium salt of each diol occurred at the PCl2 group before the fluorodiol bearing
P(OR)Cl moiety so the spiro derivatives (2, 3) formed as the major product in each
case (Figure 1).
Figure 1. The reactions of compound 1 with the diols.
Acknowledgements: The authors would like to thank Professor Christopher W. Allen (Department of
Chemistry, University of Vermont) for helpful discussions.
References:
[1] C. W. Allen, Chem. Rev., 1991, 91, 119-135.
[2] V. Chandrasekhar, V. Krishnan, Adv. Inorg. Chem., 2002, 53, 159-211.
[3] S. Beşli, C. Mutlu, F. uksel and A. l ç, Polyhedron, 2014, 81, 777-787.
Poster presentation - P089
Cis- and trans-Azole Substituted Cyclotriphosphazene Derivatives
Elif Özcan, Fatma Yuksel, Aylin Uslu*
aylin@gtu.edu.tr
Department of Chemistry
Gebze Technical University Gebze, 41400, Kocaeli-Turkey
Phosphazenes containing a framework of alternating phosphorus and nitrogen atoms
are the important class of inorganic compounds. Azole substituted phosphazenes are
attractive molecules, because of their tendency to give complexes with various
metals[1]. Most phosphazene derivatives can be synthesized via nucleophilic
substitution reactions of chlorine atoms on the chlorophosphazene with organic
nucleophiles[2]. In this study we have synthesized imidazole and benzimidazole
substituted cis- and trans-phenoxy cyclophosphazene derivatives (Figure 1).
Compounds (1a,b and 2a,b) have been characterized by mass, 31P, 1H and 13C NMR
spectroscopies. Compounds 1a, 2a, 2b have been also determined structurally by Xray crystallography.
Figure 1. Structures of the compounds 1a,b and 2a,b.
References:
[1] V. Chandrasekhar, P. Thilagar, B.M. Pandian, Coord. Chem. Rev., 2007, 251, 1045-1074.
[2] R. J. Davidson, E. W. Ainscough, A. M. Brodie, G. B. Jameson, M. R. Waterland, H. R. Allcock,
M. D. Hindenlang, Polyhedron, 2015, 85, 429-436.
Poster presentation - P090
A new insight into the homolytical bond dissociation of
Tetraaminodiphosphines
Markus Blum, Johannes Bender, Fabian Ehret, Wolfgang Frey, Sebastian Plebst,
Dietrich Gudat*
blum@iac.uni-stuttgart.de
Department of inorganic chemistry, University of Stuttgart
Pfaffenwaldring 55, GER-70569, Stuttgart
Thermally induced, homolytical P-P-bond dissociations are known for
Tetraamino-diphosphines with sterically demanding substituents.[1-2] Similar
reactivity was found for P,N heterocyclic compounds (Bisdiazaphospholenes).[3] The
thermally generated phosphinyl radicals are discussed as intermediates in the
reactions of the diphosphines with complexes, white phosphorus, and unsaturated
hydrocarbons.[4-5] In this contribution, we describe a study on the thermodynamics of
the dissociation of some diphosphines. Dissociation constants (KDiss) were determined
from quantitative EPR-Measurements[6] and allowed to calculate dissociation
enthalpies (ΔHDiss) and entropies (ΔSDiss). The results highlight importance of steric
strain for an easy P-P-bond cleavage.
Figure 1. left: EPR-Signal of (iPr2N)(Me3Si)2NP∙ from 2 0 – 340K, right: Van’t Hoff-plot
created from the analysis of the double integrals of the EPR-signals.
References:
[1] J. Bezombes, K. B. Borisenko, P. B. Hitchcock, M. F. Lappert, J. E. Nycz, D. W. H. Rankin, H.
E.Robertson, J. Chem. Soc. Dalton Trans., 2004, 1980.
[2] M. J. S. Gynane, A. Hudson, M. F. Lappert, P. P. Power, H. Goldwhite, J. Chem. Soc., Dalton
Trans., Inorg.Chem. 1980, 12, 2428.
[3] N. A. Giffin, A. D. Hendsbee, T. L. Roemmele, M. D. Lumsden, C. C. Pye, J. D. Masuda, Inorg.
Chem.,2012, 51, 11837.
[4] J. Bezombes, P. B. Hitchcock, M. F. Lappert, J. E. Nycz, Dalton Trans., 2004, 499.
[ ] D. Förster, „Zur PP-Bindungsreaktivität in unsymmetrischen und symmetrischen Nheterozyklischen Diphosphanen“, Dissertation, 2013.
[6] D. Förster, H. Dilger, F. Ehret, M. Nieger, D. Gudat, Eur. J. Inorg. Chem., 2012, 3989.
Poster presentation - P091
Synthesis of P-functional thiazole-2-thiones – precursors for NHCs?
Imtiaz Begum, Rainer Streubel*
ibegum@uni-bonn.de
Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn,
Gerhard Domagk-str.1, 53121 Bonn, Germany
Thiazole-2-thiones and their derivatives have tremendous potential in various fields,
including their medicinal and biological activities.[1] Similar to P-substituted imidazole-2-thiones[2] they also represent interesting precursors for NHCs and, hence, can
be considered as versatile ligands in metal coordination chemistry.[3] Herein, we present the synthesis of novel C-phosphanyl 2, C-phosphanoyl 3 and mixed substituted
thiazole-2-thiones 4/5 starting from 1 (Scheme). Compound 2 was converted into the
P-functional thiazolium salt 6, and via deprotonation and in situ reaction with
[Rh(cod)Cl]2 into the thiazol-2-ylidene rhodium(I) complex 7.[4] Currently, studies on
the synthesis of precursors of bis-NHCs having one (or two) phosphorus unit as linker
as well as on their reactivities are underway.
Acknowledgements: We are grateful to the DAAD for financial support PhD fellowship for I. Begum
References:
[1] D. Havrylyuka, L. Mosulaa, B. Zimenkovskya O. Vasylenkoc, A. Gzella , R. Lesyka, Eur. J. Med.
Chem. (2010), 45, 5012-5021.
[2] P. K. Majhi, S. Sauerbrey, A. Leiendecker, G. Schnakenburg, A. J. Arduengo III, R. Streubel,
Dalton Trans. 2013, 42, 13126-13136.
[3] A. J. Arduengo III, J. R. Goerlich, W. J. Marshall, Liebigs Ann./recueil, 1997, 365-374.
[4] R. Streubel, I. Begum, G. Schnakenburg, to be submitted.
Poster presentation - P092
Exploring the accessibility of thiaphosphirane complexes anew
J. Fassbender, R. Streubel*
j.fassbender@uni-bonn.de
Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität
Bonn
Gerhardt-Domagk-Str. 1, GER-53121 Bonn
While oxaphosphirane complexes[1] have received considerable interest in the last
years, only very little is known about their sulfur analogues, namely thiaphosphirane
complexes.[2] We will present the results of our attempts to synthesize thiaphosphirane
complexes III via the reaction of Li/Cl phosphinidenoid complexes I[3] with C-S πsystems, following our most recent successful[3] synthetic protocol for oxaphosphirane
complexes. Additionally, DFT studies[4] on the reaction pathways that lead to the
observed products 1, 2 as well as possible intermediates, such as the zwitterionic
complex II or the thiaphosphirane complex III, will be discussed. Furthermore, NMR
and X-ray structural data of 1 and 2 will be provided.
Acknowledgements: This work was financially supported by the DFG (STR 411/26-3), and it is
dedicated to Prof. F. Mathey.
References:
[1] (a) S. Bauer, A. Marinetti, L. Ricard, F. Mathey, Angew. Chem. Int. Ed. Engl., 1990, 29, 1166–
1167; (b) R. Streubel, A. Kusenberg, J. Jeske, P. G. Jones, Angew. Chem. Int. Ed. Engl., 1994, 33,
2427–2428.
[2] (a) E. Niecke, H.-J. Metternich, M. Nieger, D. Gudat, P. Wenderoth, W. Malisch, C. Hahner,
W.Reich, Chem. Ber., 1993, 126, 1299 – 1309; (b) R. Streubel, C. Neumann, J. Chem. Soc., Chem.
Commun., 1999, 499–500; (c) S. Maurer, T. Jikyo, G. Maas, Eur. J. Org. Chem., 2009, 2195–2207.
[3] (a) A. Özbolat, G. von Frantzius, J. Marinas Pérez, M. Nieger, R. Streubel, Angew. Chem. Intl. Ed.
Engl., 2007, 46, 9327 – 9330; (b) V. Nesterov, G. Schnakenburg, A. Espinosa, R. Streubel, Inorg.
Chem., 2012, 51, 12343–12349.
[4] R. Streubel, J. Faßbender, G. Schnakenburg, A. Espinosa Ferao, Chem. Comm., 2015, submitted.
Poster presentation - P093
1,3,5-Triphosphabenzenes: Molecules with a Thirst for Hydrogen
Rosalyn L. Falconer*, Christopher A. Russell, Douglas W. Stephan
rosalyn.falconer@bristol.ac.uk
School of Chemistry, University of Bristol
CantockÄs Close, Bristol, BS8 1TS, UK
The development of main group compounds that mimic the chemistry of transition
metals is an emerging theme in modern research.[1] Recent publications have
highlighted unexpected aspects of the reactivity of 1,3,5-triphosphabenzenes which
display pronounced transition metal-like characteristics.[2] For example, 2,4,6-tri-tertbutyl-1,3,5-triphosphabenzene reacts with hydrogen under mild conditions;
remarkably, the initial addition was shown to be reversible.[3] Furthermore, alkenes
have been shown to bind reversibly across the 1,4-sites of this heteroaromatic
substrate.[4] Clearly this significantly resembles transition metal chemistry and paves
the way for new research into the area. We have expanded investigations of the
reactivity of 1,3,5-triphosphabenzenes by studying their reactivity with other small
molecules. Across a range of chemically very different molecules (e.g., germanes,
silanes, dienes), 1,3,5-triphosphabenzenes demonstrate a remarkable ability to abstract
hydrogen from this diverse range of substrates. In this presentation, this remarkable
“thirst for hydrogen” will be explored.
Figure 1. Reversible reactivity of 1,3,5-triphosphabenzenes with hydrogen and alkenes.
References:
[1] P. P. Power, Nature 2010, 463, 171-177.
[2] R. L. Falconer, C. A. Russell, Coord. Chem. Rev., 2015, in the press, DOI:
10.1016/j.ccr.2015.02.010
[3] L. E. Longobardi, C. A. Russell, M. Green, N. S. Townsend, K. Wang, A. J. Holmes, S. B. Duckett,
J. E. McGrady, D. W. Stephan, J. Am. Chem. Soc., 2014, 38, 13453–13457.
[4] C. Peters, H. Disteldorf, E. Fuchs, S. Werner, S. Stutzmann, J. Bruckmann, C. Krüger, P. Binger, H.
Heydt and M. Regitz, Eur. J. Org. Chem., 2001, 18, 3425–3435.
Poster presentation - P094
[ClP(µ-PMes*)]2 – A Versatile Reagent in Phosphorus Chemistry
Jonas Bresien, Axel Schulz,* Alexander Villinger
jonas.bresien@uni-rostock.de
Department of Chemistry, University of Rostock
Albert-Einstein-Straße 3a, D-18059, Rostock
Ring systems composed of group 15 elements (pnictogens, Pn) are an interesting and
widely investigated field of main group chemistry.[1,2] Following our group’s specific
interest in halogen substituted cyclo-phosphanes, we started to investigate the
reactivity of dichloro-cyclo-tetraphosphane [ClP(µ-PMes*)]2 (1), whose synthesis was
recently reported.[3] Treatment of 1 with Lewis acids led to the formation of an
unprecedented bicyclic triphosphino-phosphonium ion, [Mes*P4(Cl)Mes*]+ (2+,
Figure 1).[4] In case of GaCl3, the formation of 2+ occured via a highly reactive
tetraphosphenium cation (3+), whereas use of Ag[WCA] (WCA = weakly
coordinating anion) gave rise to an intermediate dinuclear silver complex (42+). In the
presence of suitable Lewis bases, substitution of the Cl atoms was accomplished.
Depending on the sterical demand of the Lewis base, the substitution products can
either be four membered ring systems (5, 6) or diphosphene species (7) as the result of
a formal [2+2] cycloreversion reaction. Reduction of 1 with metals yielded neutral
tetraphosphabicyclobutane
Mes*P4Mes*
(8)
or
anionic
triphosphenide
[Mes*P3Mes*] (9 ), depending on the stoichiometry.
Figure 1. Product scope accessible through cyclo-tetraphosphane 1 (R = C or Pn based group).
References:
[1] M. S. Balakrishna, D. J. Eisler, T. Chivers, Chem. Soc. Rev. 2007, 36, 650–664.
[2] G. He, O. Shynkaruk, M. W. Lui, E. Rivard, Chem. Rev. 2014, 114, 7815–7880.
[3] J. Bresien, C. Hering, A. Schulz, A. Villinger, Chem. Eur. J. 2014, 20, 12607–12615.
[4] J. Bresien, K. Faust, A. Schulz, A. Villinger,
Angew. Chem. Int. Ed.
10.1002/anie.201500892.
2015,
Poster presentation - P095
Binary, Protonated Seven-Atom Zintl Anions [H2GeP6]2– and
[H2SiP6]2–
Lukas Guggolz, Stefan Mitzinger, and Stefanie Dehnen*
guggolz@chemie.uni-marburg.de
Department of Chemistry
Philipps-Universität Marburg Hans-Meerwein-Str. 4 35043 Marburg
In the course of our recent studies of group 14/15 Zintl anions as precursors for the
formation of ternary M/14/15 intermetalloid clusters,[1-4] two compounds comprising
Zintl anions that are based on the seven-atom species [GeP6]n- and [SiP6]n- were
synthesized and characterized by means of X-ray diffraction studies, mass
spectrometry, and 31P-NMR spectroscopy. The studies confirm the presence of two
[K([2.2.2]crypt)]+ counterions, which is in disagreement with the pseudo-element
concept that would accord with a 4– charge of the nortricyclan-type cages of the given
composition. For this, density functional theory (DFT) studies were applied that
served to suggest a doubly-protonated nature of the species, to determine the most
stable charge distribution as well as the most probable position of the respective group
14 element and the protons. Simultaneous optimizations of the geometric and the
electronic structure were therefore undertaken for naked clusters charged 2– and 4–,
as well as for the protonated derivatives [H2GeP6]2– and [H2SiP6]2–. In parallel, we
perform systematic studies on tetrahedral group 13/14, 13/15, and 14/15 binary Zintl
anions regarding their stability and reactivity towards organic functionalization.
Figure 1. Structure and composition of the most stable isomers of [GeP6]4– (left) and
[H2GeP6]2– (right).
References:
[1] F. Lips, R. Clérac, S. Dehnen, Angew. Chem. 2011, 123, 986–990; Angew. Chem. Int. Ed. 2011,
50, 955–959.
[2] F. Lips, S. Dehnen, Angew. Chem. 2011, 123, 991–995; Angew. Chem. Int. Ed. 2011, 50, 960–964.
[3] R. Ababei, W. Massa, K. Harms, X. Xie, F. Weigend, S. Dehnen, Angew. Chem. 2013, 125, 13786–
13790; Angew. Chem. Int. Ed. 2013, 52, 13544–13548.
[4] S. Mitzinger, L. Broeckaert, W. Massa, F. Weigend, S. Dehnen, Chem. Comm. 2015, 51, 3866–
3869.
Poster presentation - P096
Functionalization of P4 using Lewis acid-stabilized
bicyclo[1.1.0]tetraphosphabutane anions
Jaap E. Borger, Andreas W. Ehlers, Martin Lutz, J. Chris Slootweg and Koop
Lammertsma*
j.e.borger@vu.nl
Department of Chemistry and Pharmaceutical Sciences
VU University Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The
Netherlands
The direct incorporation of white phosphorus into organic fragments is a challenge
and represents an important target in organophosphorus chemistry.[1] The high
reactivity makes white phosphorus unpredictable. To allow selective conversions,
control is required.[2] A novel approach is the use of organolithium reagents. These
carbon-centered nucleophiles can open up the P4 cage and form P-C bonds. However,
these highly reactive reagents often give low selectivity and complex product
mixtures.[3, 4] The first step is believed to be the scission of one of the P-P bonds in the
P4‑tetrahedron to generate an anionic, butterfly-like bicyclotetraphosphabutane
moiety.[4b, 5] Thus far, such intermediates have not been isolated. Yet, their selective
formation is of interest as the first step in controlling the selective formation of P-C
bonds from P4. On this poster, we describe the synthesis of anionic butterfly
fragments by reacting sterically encumbered aryllithium and Lewis acids with P 4 and
discuss their reactivity.[6]
Figure 1. Synthesis and reactivity of Lewis acid stabilized bicyclotetraphosphabutane anions.
Acknowledgements: This work was supported by the Council for Chemical Sciences of the
Netherlands Organization for Scientific Research (NWO/CW)
References:
[1] (a) C.C. Cummins et al., Chem. Rev., 2010, 110, 4164; (b) M. Peruzzini et al., Chem. Rev., 2010,
110, 4178; (c) M. Scheer et al., Chem. Rev., 2010, 110, 4236.
[2] J.M. Lynam, Angew. Chem. Int. Ed., 2008, 47, 831.
[3] E. Fluck et al., Angew. Chem. Int. Ed., 1985, 24, 1056.
[4] (a) M.M. Rauhut et al., J. Org. Chem., 1963, 28, 471.; (b) J. Org. Chem., 1963, 28, 473.
[5] (a) M. Baudler et al., Angew. Chem. Int. Ed., 1988, 27, 1059. (b) F. Knoll et al., Mh. Chem., 1966,
97, 808.
[6] K. Lammertsma et al., Angew. Chem. Int. Ed., 2014, 53, 12836.
Poster presentation - P097
Fixation and liberation of intact E4 tetrahedra (E = P, As)
Fabian Spitzer and Manfred Scheer*
Fabian.spitzer@chemie.uni-regensburg.de
Institute of Chemistry, University of Regensburg
Universitätsstr. 31, 93053 Regensburg
Complexes containing tetrahedral P4 ligands represent the first step of P4 activation.[1]
Several neutral and cationic complexes with a P4 tetrahedron in η1 or η1:1 coordination
mode are known.[2] However, only few edge coordinated P4 complexes are reported,
so far.[3] Hereby two extreme cases are to be distinguished: Either electrons are
transferred to the P4 moiety or the P4 tetrahedron stays intact. For a reliable
classification computational methods are needed. A neutral complex bearing a η2- or
η2:2-coordinated P4 ligand with intact edges is still missing. Neutral examples for the
heavy analogue, yellow arsenic, are so far unknown.
We present the complexes [(LCu)2(μ,η2:2-E4)] (E = P (1a), As (1b), L = [{N(C6H3iPr22,6)C(Me)}2CH]-) containing intact E4 tetrahedra as bridging ligands. Furthermore,
we report on the formation of the mononuclear complex [ Cu(η2-P4)] (2) as the first
neutral molecule bearing an intact η2-P4 ligand. The integrity of all coordinated
tetrahedra was confirmed by DFT calculations. To prove this theoretical prediction,
the E4 ligands were substituted with the stronger Lewis-base pyridine. The released
white phosphorus and yellow arsenic could be monitored by 31P{1H} and 75As{1H}
NMR spectroscopy, respectively.
References:
[1] a) B. M. Cossairt, N. A. Piro, C. C. Cummins, Chem. Rev. 2010, 110, 4164-4177; b) M. Caporali,
L. Gonsalvi, A. Rossin, M. Peruzzini, Chem. Rev. 2010, 110, 17 - 23 c) M. Scheer, G. Balázs, A.
Seitz, Chem. Rev. 2010, 110, 4236-4256; d) S. Khan, S. S. Sen, H. W. Roesky, Chem. Commun. 2012,
48, 2169-2179; e) N. A. Giffin, J. D. Masuda, Coord. Chem. Rev. 2011, 255, 1342-1359.
[2] a) S. Heinl, E. V. Peresypkina, A. Y. Timoshkin, P. Mastrorilli, V. Gallo, M. Scheer, Angew. Chem.
Int. Ed. 2013, 52, 10887-10891; b) T. Gröer, G. Baum, M. Scheer, Organometallics 1998, 17, 59165919; c) V. Mirabello, M. Caporali, V. Gallo, L. Gonsalvi, D. Gudat, W. Frey, A. Ienco, M. Latronico,
P. Mastrorilli, M. Peruzzini, Chem. Eur. J. 2012, 18, 11238-11250.
[3] a) I. Krossing, L. van Wüllen, Chem. Eur. J. 2002, 8, 700-711; b) G. Santiso-Quinones, A.
Reisinger, J. Slattery, I. Krossing, Chem. Commun. 2007, 5046-5048; c) L. C. Forfar, T. J. Clark, M.
Green, S. M. Mansell, C. A. Russell, R. A. Sanguramath, J. M. Slattery, Chem. Commun. 2012, 48,
1970-1972.
Poster presentation - P098
Functionalization of [Cpʹʹ2Zr(1:1-P4)]
Andreas E. Seitz, Manfred Scheer*
andreas-erich.seitz@ur.de
Institute of Inorganic Chemistry, University of Regensburg,
Universitätsstraße 31, GER-93053, Regensburg
In the past few years, the activation and functionalization of white phosphorus as well
as the transfer of phosphorus units became a central area of research in the field of
Inorganic Chemistry.[1] A reasonable approach to study the stepwise degradation of P4
is the functionalization of P4 butterfly complexes. Herein, we report on the reaction of
[Cpʹʹ2Zr(1:1-P4)] with tert-Butyllithium at low temperature and subsequent reactions.
References:
[1] Recent Reviews on P4 activation: a) B. M. Cossairt, N. A. Piro, C. C. Cummins, Chem. Rev. 2010,
110, 4164-4177; b) M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem. Rev. 2010, 110, 41784235; c) M. Scheer, G. Balázs, A. Seitz, Chem. Rev. 2010, 110, 4236-4256.
Poster presentation - P099
Synthesis and Application of Weighable Brønsted Acids Containing
Hexacoordinated Phosphorus(V) Anions
K. Hazin, P.W. Siu, D.P. Gates*
khazin@chem.ubc.ca
Department of Chemistry, University of British Columbia,
2036 Main Mall, Vancouver, BC, Canada V6T 1Z1
The development of solid, weighable Brønsted acids is of particular interest due to
their potential use in bond activation reactions.1 However, systems of the type H+[X]are not generally isolable due to the inherent high reactivity of most anions with H +.
The bonding nature of weakly coordinating anions (WCA) facilitates the successful
isolation of Brønsted acids and plays a critical role in the generation and stabilization
of highly reactive cations. Our research focuses on employing the known charge
balancing tris(tetrachlorobenzenediolato)phosphate anion (TRISPHAT, [1]-)2 to
afford a novel class of isolable Brønsted acids. The synthesis and characterization of
the solid, weighable HL2[1] (Figure 1, L = donor solvent) will be discussed.3 In
addition, the application of HL2[1] as an effective single-component initiator for the
carbocationic polymerization of vinyl monomers at a variety of temperatures and
monomer-to-initiator ratios will be surveyed.
Figure 1. Cationic olefin polymerization with hexacoordinated phosphorus(V) anion.
References:
[1] (a) R.J. Phipps, G.L. Hamilton, F.D. Toste, Nature Chemistry 2012, 4, 603-614; (b) I. Krossing, I.
Raabe, Angew. Chem. Int. Ed. Engl. 2004, 43, 2066-2090.
[2] J. Lacour, C. Ginglinger, C. Grivet, G. Bernardinelli, Angew. Chem. Int. Ed. Engl. 1997, 36, 608610.
[3] (a) P.W. Siu, K. Hazin, D.P. Gates, Chem. Eur. J. 2013, 27, 9005-9014; (b) P.W. Siu, D.P. Gates,
Can. J.Chem. 2012, 90, 574-583; (c) P. W. Siu, D.P. Gates, Organometallics 2009, 28, 4491-4499.
Poster presentation – P100
N-Trimethylsilylsulfinylamine - Reactivity and Isomerisation
Induced by Lewis Acids
René Labbow, Axel Schulz,* and Alexander Villinger
rene.labbow@uni-rostock.de
Department of Chemistry, University of Rostock
Albert-Einstein-Straße 3a, D-18059 Rostock
Sulfinylimine HNSO was probably first discovered by F. Ephraim and H. Piotrowski
in 1911.[1,2] Its low boiling point below –60°C renders this compound impractical for
applied chemistry. Substitution of the proton against a Me3Si group led to the title
compound.[3,4] We will report of Lewis acid assisted isomerisation of this
sulfinylamine to a siloxathiazate 1 (Figure 1 right). Our investigations refer to the
reaction presented in Figure 1 using different classical Lewis acids like gallium
trichloride GaCl3or the more sterically demanding borane B(C6F5)3as well as highly
reactive species like the trimethylsilyl cation [Me3Si]+. In this manner, different
Lewis acids led on different pathways to the formation of adducts (pathway A),
adducts of the isomeric sulfanylidyneamine -OSN (pathway B) or a homoleptic cation
(pathway C). These precursors can be used to build up heterocyclic compounds
containing sulfur, nitrogen and oxygen or any combination of these elements.[5]
Figure 1: Left: reaction pathways, right: molecular structure of 1.
References:
[1] F. Ephraim, H. Piotrowski, Chem. Ber. 1911, 44, 379–386.
[2] P. W. Schenk, Chem. Ber. 1942, 75, 94–99.
[3] O. J. Scherer, P. Hornig, Angew. Chem. Int. Ed. 1966, 5, 729–730.
[4] K. I. Gobbato, C. O. Della Védova, H. Oberhammer, J. Mol. Struct. 1995, 350, 227–231.
[5] S. I. Bell, M. Parvez, S. M. Weinreb, J. Org. Chem. 1991, 56, 373–377.
Poster presentation – X101
Synthesis and Reactivity of a Triflyloxyphosphonium Dication
Sivathmeehan Yogendra,(a) Felix Hennersdorf,(a) Antonio Frontera,(b) Roland
Fischer(c) and Jan J. Weigand(a)*
Sivathmeehan.Yogendra@chemie.tu-dresden.de
Department of Chemistry and Food Chemistry
(a) Department of Chemistry and Food Chemistry, TU Dresden,
Mommsenstrasse 4, GER-01162, Dresden
(b) Departament of Chemistry, Universitat de les Illes Balears
(c) Department of Inorganic Chemistry, TU Graz
N-heterocyclic carbenes (NHCs)[1] and cyclopropenylidenes (CPDs)[2] have been
proven to be powerful ligands facilitating the stabilization of highly reactive, cationic
P-derivatives. In this context, carbodiphosphoranes (CDPs) are an interesting class of
ligands due to their expected enhanced stabilization effects as the result of their
additional π-donor properties. This was recently demonstrated by the use of (Ph3P)2C
as a valuable ligand in the synthesis of a low-coordinated P(III)-dication.[3] Therefore,
we are currently investigating (Ph3P)2C as a suitable ligand for the synthesis of
electron deficient phosphonium salts. The two step reaction of 1[OTf] with i) tBuO2H
and ii) Tf2O affords the triflyloxyphosphonium dication 2+ as triflate salt in high
yield. The presence of the (Ph3P)2C-substituent renders an unusual reactivity of
compound 2[OTf]2 by featuring two electrophilic reaction sides. As an example,
heating 2[OTf]2 at elevated temperature (~ 200 °C) leads to the elimination of HOTf
accompanied with the formation of 3[OTf]2. Further unusual transformation reactions
are presented in this poster.
References:
[1] (a) M. H. Holthausen, M. Mehta, D. W. Stephan, Angew. Chem. Int. Ed. 2014, 53, 6538;(b) K.
Schwedtmann, M. H. Holthausen, K.-O. Feldmann, J. J. Weigand, Angew. Chem. Int. Ed. 2013, 125,
14204; (c) J. J. Weigand, K.-O. Feldmann, F. D. Henne, J. Am. Chem. Soc. 2010, 132, 16321.
[2] (a) J. Petuŝkova, M. Patil, S. Holle, C. W. ehmann, W. Thiel, M. Alcarazo, J. Am. Chem. Soc.
2011, 133, 20758.
[3] M. Q. Y. Tay, Y. Lu, R. Ganguly, D. Vidović, Angew. Chem. Int. Ed. 2013, 52, 3132.
Poster presentation – X102
Synthesis and Structure of Terdentate Ketoiminate Complexes
Roman Olejník, Zdeňka Růžičková, Jan Merna, Aleš Růžička
roman.olejnik@upce.cz
University of Pardubice, Faculty of Chemical Technology, Department of General
and Inorganic Chemistry
Studentská 573, CZ-532 10 Pardubice, CzechRepublic
The coordination chemistry of the group 12-14 elements has attracted a significant
interest in particular due to remarkable reactivity and possible wide range of
applications starting from organic transformations[1] to various polymerizations
reactions[2]. Terdentate ketoiminate may be classified among the most widespread
spectator systems which can stabilize metal centers and thus form six membered
metallacycles. The central fragment consists of NC3O skeleton and renders space for
variation a number of its substituents or could by formally a part of hetero/aromatic
rings and also nitrogen atom could be substituted by different entities with tunable
steric demand and character. The preparation of target complexes can be classified
into two main reaction procedures. The first one is transmetallation of deprotonated
ketoimine species with metal halogenide MCl2(M = Sn(II), Ge(II) and Zn(II)). The
other pathway is protolithic reaction of a pro-ligand and an appropriate reactive
compound such as metal bisamide (M[N(TMS)2]2, M(II) = Ge, Sn) or metal alkyls
(MR n , M = Zn(II), Al(III); R = Me, Et), which produced desired products via an
amine or alkyl elimination route. Obtained complexes (Figure 1) were used for further
tests of its reactivity or as co-initiators for co/polymerization reactions (εcaprolactone, trimethylene carbonate etc.). Comprehensive study of tetrylene
complexes is supported by quantum chemistry calculations.
Figure 1. The molecular structure of one of the compounds studied.
Acknowledgements: We gratefully acknowledged the financial support of the Czech Science
Foundation (project no. P207/11/0705).
References:
[1] M. Asay, C. Jones, M. Driess,Chem. Rev., 2011, 111, 354-396.
[2] N. M. Rezayee, K. A. Gerling, A. L. Rheingold, J. M. Fritsch, Dalton Trans., 2013, 42, 5573-5586.
Poster presentation - P103
A Novel Synthesis of the 2-Phosphaethynolate Anion and Subsequent
Reactivity
Andrew R. Jupp, Jose M. Goicoechea*
andrew.jupp@chem.ox.ac.uk
Department of Chemistry, University of Oxford
12 Mansfield Rd, Oxford, OX1 3TA, UK
Expanding on previous research on the activation of [P7]3– by unsaturated
molecules,[1] we report that the heptaphosphide trianion reacts with ambient pressures
of carbon monoxide to form the phosphaethynolate anion, PCO–.[2] This phosphorus
containing analogue of the ubiquitous cyanate anion has been the subject of a number
of recent articles by our group and those of Grützmacher and Cummins.[3,4] We have
systematically explored the ligand properties and cycloaddition chemistry of PCO–
towards a range of heteroallenes, yielding several novel heterocycles.[2] Furthermore,
by analogy with Wöhler’s paradigm-shifting synthesis of urea in 1828, the reaction of
>PCO– with ammonium salts yields the unprecedented phosphinecarboxamide.[5] This
inorganic analogue of urea is a rare example of an airstable primary phosphine, and its
ligand properties have been explored.[6] We have also explored its Brønsted acidity to
afford a series of novel phosphides, secondary and tertiary phosphines, and phosphine
oxides.[7]
Figure 1. Formation of novel anionic P-containing heterocycles from PCO–.
Acknowledgements: We thank the University of Oxford and EPSRC for funding.
References:
[1] R. S. P. Turbervill, J. M. Goicoechea, Chem. Rev. 2014, 114, 10807.
[2] A. R. Jupp, J. M. Goicoechea, Angew. Chem., Int. Ed. 2013. 52, 10064.
[3] F. F. Puschmann, D. Stein, D. Heift, C. Hendriksen, Z. A. Gal, H.-F. Grützmacher, H. Grützmacher,
Angew. Chem. Int. Ed. 2011, 50, 8420.
[4] I. Krummenacher, C. C. Cummins, Polyhedron, 2012, 32, 10.
[5] A. R. Jupp, J. M. Goicoechea, J. Am. Chem. Soc. 2013, 135, 19131.
[6] M. B. Geeson, A. R. Jupp, J. E. McGrady, J. M. Goicoechea, Chem. Commun. 2014, 50, 12281.
[7] A. R. Jupp, G. Trott, É. Payen de la Garanderie, J. D. G. Holl, D. Carmichael, J. M. Goicoechea,
Chem. Eur. J. Manuscript accepted for publication
Poster presentation - P104
Pentaphospha- and Pentaarsaferrocene
A Comparative Study of Their Coordination Ability Towards
Weakly Coordinating Lewis Acids
Martin Fleischmann, Manfred Scheer*
Martin.fleischmann@ur.de
Institute of Inorganic Chemistry, University of Regensburg
Universitätsstraße 31, GER-93053, Regensburg
During the last decades supramolecular chemistry based on weak interactions like
hydrogen bonds, van der Waals interactions or weak dative bonds instead of strong
covalent bonds has gained more and more attention. In this context, we are
investigating the coordination chemistry of heavier Group 15 element ligands. The
discovery of the all-phosphorus and all-arsenic analogue of the well-known
cyclopentadienyl ligand in [Cp*Fe(η5-E5)] (E = P, As) by Scherer et al. about twenty
years ago can be viewed as a milestone in organometallic chemistry.[1] These
complexes contain a subtituent-free planar E5 ring which enables them to act as
ligands in coordination chemistry themselves. While the reaction of the cyclo-P5
complex with CuI halides leads to fullerene-like spherical supermolecules[2] and
capsules,[3] similar reactions of the analogues cyclo-As5 complex result in polymeric
compounds.[4] These investigations reveal a preferred π-coordination for As instead of
a σ-coordination in the case of P.
This poster presents the interaction of the Lewis acids Ag+ and Tl+ with the cyclo-E5
rings of pentaphospha- and pentaarsaferrocene. Selected examples show
unprecedented bonding modes and enable a direct comparison of these complexes.
Figure 1. Different coordination of the cyclo-P5 and cyclo-As5 complexes towards Ag+.
References:
[1] (a) O. Scherer, T. Brück, Angew. Chem. Int. Ed. 1987, 26, 59; Angew. Chem. 1987, 99, 59. (b) O.
Scherer, C. Blath, G. Wolmershäuser, J. Organomet. Chem. 1990, 387, C21.
[2] J. Bai, A. Virovets, M. Scheer, Science 2003, 300, 781.
[3] S. Welsch, C. Gröger, M. Sierka, M. Scheer, Angew. Chem. Int. Ed. 2011, 50, 1435; Angew. Chem.
2011, 123, 1471.
[4] H. Krauss, G. Balázs, M. Bodensteiner, M. Scheer, Chem. Sci. 2010, 1, 337.
Poster presentation - P105
Chemistry of Cationic Arsines: A New Class of Electrophilic Ligands
Jonathan W. Dube, Manuel Alcarazo
dube@kofo.mpg.de
Department of Organometallic Chemistry
Max Planck Institut für Kohlenforschung, Kaiser-Wilhelm-Platz-1, DE-45470,
Mülheim an der Ruhr
Finely tuning the structure and design of ligands is a critical component to the
development of new transition-metal mediated processes. While the synthesis of new
phosphine and carbene compounds is an active area of investigation, the extension of
ligand design to arsenic is relatively unexplored. This is despite the fact that arsines
are known to be poorer σ–donors and π–acceptors when compared to phosphines,
which could be useful for a number of catalytic reactions.1 In this context, this
presentation will focus on our efforts in cationic arsine chemistry, as an extension of
our interest in polycationic phosphines (ie. A-C).2 A novel arsenic proligand with a
cationic cyclopropenium substituent (1) is prepared in high yields and is indefinitely
air and moisture stable. Despite being highly electrophilic, 1 is capable of forming a
number of bottleable transitional metal complexes, for example with gold (2),
platinum, and palladium (3). This is contrary to conventional electron-poor arsines (ie.
AsF3, As(C6F5)3), which do not coordinate to these elements. In addition to this
remarkable coordination chemistry, the chemical oxidation with XeF2(4), preparation
of other derivatives, and application in π–acidic catalysis will be discussed.
Figure 1. Structures of representative arsenic compounds to be described.
Acknowledgements: The authors are extremely grateful for the funding and excellent departments
(NMR, X-ray, Mass) provided by the MPI. Financial support for this work was also provided by Max
Planck Gesellschaft and the Deutsche Forschung Gemeinschaft.
References:
[1] (a) A. Fürstner, P. W. Davies, Angew. Chem. Int. Ed., 2007, 46, 3410; for an early example see (b)
V. Farina, B. Krishnan, J. Am. Chem. Soc., 1991, 113, 9585.
[2] M. Alcarazo, Chem. Eur. J., 2014, 26, 7868.
Poster presentation - P106
Reaction of the Lewis acid B(C6F5)3 with [Ph3SbO]2, Ph2P(O)OH and
other Lewis bases containing oxygen acceptor atoms
Ralf Kather, Enno Lork, Matthias Vogt, Jens Beckmann*
ralfkather@gmx.de
Institut für Anorganische Chemie
Universität Bremen Leobener Str, GER-28359, Bremen
The Lewis acid B(C6F5)3has found numerous applications as catalyst, e.g. for the
homogenous olefin polymerization or the FLP activation of small molecules.[1,2] With
triorganophosphine oxides, it has been also used to prepare archetypical Lewis pair
complexes, such as Ph3POB(C6F5)3.[3] We have recently shown that the previously
known dimeric (Ph3SbO)2can be disaggregated by B(C6F5)3giving rise to the
formation of the analogous Ph3SbOB(C6F5)3(1) having a short bipolar single +Sb-OB– bond (see Figure).[4] The closely related reaction of B(C6F5)3with the weak
Brønsted acid Ph2P(O)OH provided in situ the metastable acid HOPPh2OB(C6F5)3(2),
the reactivity of which has been elaborated. In absence of other substrates it
undergoes autoprotolysis affording eight-membered boraphosphinate ring
[Ph2POB(C6F5)2O]2(3) and C6F5H (see Figure).[5] In the presence of the polymeric
[Ph2SnO]nthe eight-membered Sn2P2O4 heterocycle [Ph2Sn(OPPh2O)2SnPh2]
[HOB(C6F5)3]2(4) was formed.[5] In the reaction with Ph4Sn, phenyl group cleavage
takes place and Ph3SnOPPh2O(B6F5)3(5) was obtained.
Figure 1. Molecular structures of Ph3SbOB(C6F5)3 (1), [Ph2POB(C6F5)2O]2 (3), and
[Ph2Sn(OPPh2O)2SnPh2][HOB(C6F5)3]2 (4).
References:
[1] W. E. Piers, T. Chivers, Chem. Soc. Rev., 1997, 26, 345.
[2] D. W. Stephan, G. Erker, Angew. Chem. Int. Ed., 2010, 49, 46.
[3] M. A. Beckett, D. S. Brassington, M. E. Light, M. B. Hursthouse, J. Chem. Soc., Dalton Trans.,
2001, 11, 1768.
[4] R. Kather, T. Svoboda, M. Wehrhahn, E. Rychagova, E. Lork. L. Dostal, S. Ketkov, J. Beckmann,
Chem. Commun., 2015, 51, 5932.
[5] R. Kather, E. Lork, E. Rychagova, S. Ketkov, J. Beckmann, Manuscript in preparation.
Poster presentation - P107
Polycyclic Amides with As and Sb
L. Belter, W. Frank*
Lukas.Belter@hhu.de
Institut für Anorganische Chemie und Strukturchemie, Lehrstuhl II: Material- und
Strukturforschung, Heinrich Heine Universität
Universitätsstraße 1, GER-40225, Düsseldorf
Polycyclic and cage-like amides of As, Sb and Bi are still very rare, especially those
containing more than one of these elements. The first polycyclic amide containing
both the elements As and Sb (4) was synthesized in 1994 by M. Veith et al. via
classical salt elimination reaction.[1] 4 as well as further compounds with different
substitution patterns were now successfully synthesized by the reaction of
diazarsasiletidines (1-3) with SbF3. Compounds 4-6 show an unusual 3+1coordination of the Sb atom including a secondary Sb···N interaction.
Figure 1. Synthesis and crystal structures of polycyclic amides of As and Sb (4-6).
References:
[1] M. Veith, A. Rammo, M. Hans, Phosphorus, Sulfur Silicon Relat. Elem. 1994, 93, 197-200.
Poster presentation - P108
The reactivity of As4 towards transition metal complexes
Monika Schmidt, Manfred Scheer*
Monika.Schmidt@ur.de
Institute of Inorganic Chemistry, University of Regensburg
Universitätsstraße 31, GER - 93053 Regensburg
Over the last few years, the activation of white phosphorus or yellow arsenic is in
focus of current chemistry. Here, not only the degradation of the E4 tetrahedron is
observed, also reaggregation proceeds. In the case of white phosphorus, a wide
variety of substituent free Pn ligand complexes has been synthesized.[1] In contrast,
yellow arsenic is not easy to handle especially due to its sensitivity to light. Therefore,
only few results of As4 activation with transition metal fragments are reported.[2] Most
of these Asn ligand complexes are synthesized by cothermolysis reactions at high
temperatures. Thereby, cyclopentadienyl containing carbonyl complexes are often
used as starting materials.
Herein we report on the activation of As4 with transition metals. Furthermore the
sterically demanding cyclopentadienyl ligand CpBn (CpBn = pentabenzylcyclopentadienyl) is introduced in this chemistry in order to receive unprecedented structural
motifs. We succeeded, for instance, in synthesizing [(CpBnMo)2(µ,η5:5:1:1-As10)] by
cothermolysis of [CpBnMo(CO)2]2 with As4.
References:
[1] a) B.M. Cossairt, N. A. Piro, C. C. Cummins, Chem. Rev. 2010, 110, 4164-4177. b) M. Caporali. L.
Gonsalvi, A. Rossin, M. Peruzzini, Chem. Rev. 2010, 110, 4178-4235. c) M. Scheer, G. Balázs, A.
Seitz, Chem. Rev. 2010, 110, 4236-4256.
[2] a) O. J. Scherer, Angew. Chem. 1990, 102, 1137-1155. b) O. J. Scherer, Acc. Chem. Res 1999, 32,
751-762.
Poster presentation - P109
Stibinidine and Bismuthinidine as ligands for TM
Iva Vránová , Zdeňka Růžičková, Milan Erben, Libor Dostál
st20166@student.upce.cz
Department of General and Inorganic Chemistry, University of Pardubice
Studentská 95, CZE-53210, Pardubice
TM complexes of sub(low)-valent p-block element compounds have attracted
considerable attention not only because of their unique structures, but also in the
regard to their synthetic potential in organometallic chemistry. Our group has recently
succeeded in the synthesis and structural characterization of the first monomeric
stibinidene and bismuthinidene stabilized by an effective coordination of the N,C,Npincer type ligand.[1] The main drawback of this investigation was both relatively
complicated synthesis of the N,C,N-ligand precursor and low yields of these lowvalent products observed after reduction of trivalent precursors. For these reasons, we
modified the ligand backbone and we obtain new monomeric stibinidenes and
bismuthinidenes. These monovalent RE(I) (E = Sb, Bi) species contain two electron
lone pairs available for TM coordination (Figure 1). In this work the reactivity of
monovalent stibinidenes and bismuthinidenes with selected TM complexes will be
presented.
Figure 1: Coordination coordination capability of titled stibinidenes and bismuthinidenes.
Acknowledgements: The authors thank the Grant agency of Czech Republic project no. P207/1506609S.
References:
[1] P. Simon, F. de Proft, R. Jambor, A. Ruzicka, L. Dostal, Angew. Chem. Int-Ed., 2010, 49, 54685471.
Poster presentation - P110
Using Supramolecular Interactions to shape new Halogenido
Bismuthate Materials
Johanna Heine
johanna.heine@chemie.uni-marburg.de
Fachbereich Chemie, Philipps-Universität Marburg
Hans Meerwein Straße, 35043, Marburg
Interest in main group metal halogenido metalates has recently surged with perovskite
based materials as a new candidate for solar cells.[1] Yet, while this has generated a
flurry of activity in the field of stannates and plumbates, the related bismuthates also
hold great potential for new materials with useful properties such as ferroelectricity or
photoluminescence.[2] It has been our goal to evolve the functionality of these
materials by using cations capable of extended supramolecular interactions. Using
alkali metal crown ether adducts, extended viologens or metalloviologenes as cationic
building blocks, we have obtained a host of new halogenido bismuthate materials and
studied their optical properties – from basic absorption and emission characteristics to
their thermo- and photochroism.
Figure 1. Combined thermo- and photochromism in halogenido bismuthate materials.
References:
[1] B. V. Lotsch, Angew. Chem. Int. Ed., 2014, 53, 635- 637.
[2] (a) N. Leblanc, N. Mercier, L. Zorina, S. Simonov, P. Auban-Senzier, C. Pasquier, J. Am. Chem.
Soc., 2011, 133, 14924-14927.; (b) G. Xu, G.-C. Guo, J.-S. Guo, S.-P. Guo, X.-M. Jiang, C. Yang, M.S. Wang, Z.-J. Zhang, Dalton Trans., 2010, 39, 8688-8692.
Poster presentation - P111
Syntheses of Binary Interpnictogenes and their Reactivity
Benjamin Ringler, Carsten von Hänisch*
benjamin.ringler@chemie.uni-marburg.de
Department of Chemistry
Philipps-Universität Marburg Hans-Meerwein-Straße 4 GER-35032, Marburg
On the poster we present syntheses of novel stibano amines. Additionally we
investigate the reactivity of di‑tbutylstibano amine towards AlEt3and InEt3to achieve
stibane substituted N2Al2/N2In2four rings.[1],[2] We discovered an access to novel
binary interpnictogenes by converting di‑tbutylstibano chloride with lithiated primary
amines to yield a fully tbutyl substituted amino stibane 1 and an ipropyl analogous 2.
Furthermore stibano amines 3 and 4 can be obtained by reaction with lithium amide
under different conditions. A condensation from 4 to 3 is observed while ammonia is
formed. Compound 4 and AlEt3/InEt3are converted to [tBu2SbN(H)AlEt2]25 and
[tBu2SbN(H)InEt2]26. We obtained the first examples where a nitrogen atom is
connected to both antimony and aluminium/indium. Besides that antimony substituted
Al2N2/In2N2four rings are a novelty among the well-known Al2N2/In2N2ring systems.
Figure 1. Reaction of a chloro stibane with amides to form stibano amines 1-4 and molecular
structures of 5 and 6.
Acknowledgements: DFG-Graduiertenkolleg “Funktionalisierung von Halbleitern“
References:
[1] B. Ringler, Master‘s thesis, Marburg, 2014.
[2] B. Ringler, C. von Hänisch, manuscript in preparation.
Poster presentation - P112
Investigating non-covalent interactions in crowded frameworks by
77
Se and 125Te solid-state NMR
Paula Sanz Camacho, Fergus R. Knight, Kasun S. Athukorala Arachchige, Daniel
Dawson, Alexandra M. Z. Slawin, Jonathan R. Yates, J. Derek Woollins, and Sharon
E. Ashbrook.
Jdw3@st-and.ac.uk
EaStCHEM School of Chemistry, St Andrews
School of Chemistry , University of St Andrews, Fife KY16 9ST UK
Non-covalent interactions are not as well studied as strong covalent and ionic
bonding, and are still the focus of some controversy. However, these interactions are
important as they can affect thermodynamic stability, molecular geometry, crystal
packing, reactivity etc... of the compounds in which they occur. Naphthalene and
acenaphthenes systems provide good models to study this type of interaction, as two
large heteroatoms are constrained in the peri-positions of a rigid organic backbone. In
this situation, in order to stabilize the steric hindrance that occurs between the heavy
atoms, a weak interaction and/or distortion of the geometry is observed.1 In this work,
we investigate not just intramolecular interactions between mixed peri-substituted
acenaphthenes, shown in solution and in the solid-state by 77Se and 125Te solid-state
NMR2, but also an unusual intermolecular interaction that occurs between two
molecules (novel chalcogen-phosphorus heterocycles) that are packed such as the SeP distance smaller than the van der Waals radii. 77Se, 125Te and 31P results will be
shown, together with DFT calculations, to understand the origin of these interactions.
Furthermore, analysis of many of the compounds reveals significant polymorphism,
not observed in the original single crystal diffraction data. The nature of the
polymorphism present is then confirmed by a combination of solid-state NMR
experiments, high-throughput „robot-based“ crystallography of a number of single
crystals and first-principles calculations.
Figure 1. SSNMR and crystal structures of the new Compounds.
References:
[1] Aschenbach, L. K.; Knight, F. R.; Randall, R. A. M.; Cordes, D. B.; Baggott, A.; Buhl, M.; Slawin,
A. M. Z., Woollins, J. D. Dalton Trans. 2012, 41, 3141.
[2] Stanford, M. W.; Knight, F. R.; Athukorala Arachchige, K. S.; Sanz Camacho, P.; Ashbrook, S. E.;
Bühl, M.; Slawin, A. M. Z.; Woollins, J. D. Dalton Trans. 2014, 43, 6548.
Poster presentation - P113
Supramolecular Interactions of 1,2,5-Selenadiazole Derivatives
Lucia M. Lee, I. Vargas-Baca*
leem35@mcmaster.ca
Department of Chemistry & Chemical Biology, McMaster University, Hamilton
1280 Main St. W Hamilton, ON, Canada L8S 4M1
Recent literature denotes a remarkable surge of interest in supramolecular interactions
mediated by heavy p-block elements, “halogen bonding” is just a prominent example.
While the σ‑hole model emphasizes the electrostatic component, covalent
(polarization) and dispersion contributions also play a significant role in this
phenomenon. All these factors are strongest for the heaviest elements. Indeed,
compounds of tellurium very frequently form strong intermolecular links[2]. However,
the strength of their supramolecular bonds can be manipulated by adjusting the
electron acceptor ability of selenium. This is most efficiently accomplished by
attachment, either formal or actual, of a Lewis acid[4] to one of the nitrogen atoms. We
will present an overview of our systematic investigations and application of this
approach to induce selenadiazoles to engage in supramolecular interactions. It
includes the synthesis and structural characterization of transition-metal coordination
polymers
Figure 1. Supramolecular structures based on benzo-2,1,3-selenadiazole.
Acknowledgements: The support of the NSERC Canada is gratefully acknowledged. Part of this work
was made possible by the facilities of the Shared Hierarchical Academic Research Computing Network
(SHARCNET: www.sharcnet.ca) and Compute/Calcul Canada.
References:
[1] (a) A. F. Cozzolino, P. J. W. Elder, I. Vargas Baca, Coord. Chem. Rev. 2011, 255, 1426–1438. (b)
A.F. Cozzolino, I. Vargas Baca, J. Organomet. Chem. 2007, 692, 2654–2657.
[2] A. F. Cozzolino, I. Vargas Baca, S. Mansour, A. H. Mahmoudkhani, J. Am. Chem. Soc. 2005, 127,
3184–3190.
[3] (a) L. M. Lee, P. J. W. Elder, A. F. Cozzolino, Q. Yang, I. Vargas Baca, Main Group Chem. 2010,
9, 117–133. (b) Cozzolino, A. F.; Elder, P. J. W.; Lee, L. M.; Vargas Baca, I. Can. J. Chem. 2013, 91,
338–347.
[4] (a) M. Risto, R. W. Reed, C. M. Robertson, R. Oilunkaniemi, R. S. Laitinen, R. T. Oakley, Chem.
Commun. 2008, 3278–3280. (b) G. Berionni, B. Pégot, J. Marrot, CrystEngComm 2009. 11, 986. (c) J.
L. Dutton, J. J. Tindale, M. C. Jennings, P. J. Ragogna, Chem. Commun. 2006, 2474–2476.
[5] L. M. Lee, P. J. W. Elder, P. A. Dube, J. E. Greedan, H. A. Jenkins, J. F. Britten, I. Vargas Baca,
CrystEngComm. 2013, 15, 7434–7437.
Poster presentation - P114
Exploring new anionic selenium based pincer ligands
Bronte J. Charette, Jamie S. Ritch*
charettb@myumanitoba.ca
Department of Chemistry, The University of Winnipeg; University of Manitoba
599 Portage Ave., R3B 2G3, Winnipeg, Manitoba, Canada Parker Building, R3T 2N2,
Winnipeg, Manitoba, Canada
The focus of this work lies in the synthesis, characterization and coordination of a
series of anionic pincer ligands that contain selenium. Selenium and tellurium are soft
Lewis bases that exhibit strong electron donor properties, and in conjunction with the
hard Lewis base, nitrogen, should exhibit diverse new coordination chemistry. There
are numerous examples of pincer ligands with phosphorus, nitrogen and carbon as
donor atoms, but few examples exist of selenium and tellurium containing pincer
ligands.[1] Transition metal complexes of such ligands have shown the potential to
outperform their sulfur and phosphorus analogues as catalysts in the Heck reaction.[2]
Such improvements could include promoting catalytic activity in more cost efficient
metal complexes based on iron and nickel, compared to costly palladium. This
presentation will focus on the synthesis and characterization of a new Se-N-Se pincer
ligand based on a known PNP analogue.[3] The attempted coordination chemistry of
this complex with transition metals will also be discussed.
References:
[1] Kumar, A.; Rao, G. K.; Saleem, F.; Singh, A. K. Dalton Trans. 2012, 41, 11949-11977.
[2] Yao, Q.; Kinney, E.; Zheng, C. Org. Lett. 2004, 6, 2997-2999.
[3] Fryzuk. M. D.; Inorg. Chem. 1982,21, 2134-2139.
Poster presentation - P115
Coordination and Reduction of 1,2,5-Telluradiazole Heterocycles
Nikolay A. Pushkarevsky*, Denis S. Grigoriev, Nikolay A. Semenov, Sergey N.
Konchenko, Jens Beckmann, Andrey V. Zibarev
nikolay@niic.nsc.ru
Nikolaev Institute of Inorganic Chemistry SB RAS
Akademika Lavrentieva str. 3, 630090 Novosibirsk, Russia
Chemistry of 1,2,5-telluradiazoles is intensely studied in the last decade. Despite
molecular similarities to their S- and Se-containing analogs, they are largely different
from those in structural aspects and reactivity. In condensed state they tend to form
[Te2N2] secondary bonding units which are preserved upon formation of chargetransfer complexes[1] and, partly, upon coordination of the Te atom. In the case of
chelating ligands (e. g. diamines), coordination polymers containing mono- or dimeric
tellurodiazole units are formed (Fig. 1). Another contrast feature is the reduction
processes, where thiadiazoles are known to form stable radical anions (RA)[2]. Stable
telluradiazolyl RA are not known to date, while action of common reducing agents
often results in the formation of species, apparently not containing RA. We present
the latest data on the coordination of different types of neutral ligands (amines,
phosphines, carbenes) to the Te atom of telluradiazole ring. Reaction behavior of
telluradiazole systems with some reducing agents, as well as possible reaction
pathways are discussed.
Figure 1. Two products of coordination of dicyanotelluradiazole with TMEDA (left); scheme
of reduction of benzotelluradiazole (right), with the product of partial decomposition.
Acknowledgements: The authors are grateful to the Russian Foundation for Basic Research (grant No.
13-03-01088) and to the Deutsche Forschungsgemeinschaft (project BE 3716/3-1) for financial
support.
References:
[1] N. A. Pushkarevsky, A. V. Lonchakov, N. A. Semenov, E. Lork, L. I. Buravov, L. S.
Konstantinova, G. T. Silber, N. Robertson, N. P. Gritsan, O. A. Rakitin, J. D. Woollins, E. B.
Yagubskii, J. Beckmann, A. V. Zibarev, Synthetic Met.,2012, 162, 2267–2276.
[2] N. A. Semenov, N. A. Pushkarevsky, E. A. Suturina, E. A. Chulanova, N. V. Kuratieva, A. S.
Bogomyakov, I. G. Irtegova, N. V. Vasilieva, L. S. Konstantinova, N. P. Gritsan, O. A. Rakitin, V. O.
Ovcharenko, S. N. Konchenko, A. V. Zibarev, Inorg. Chem., 2013, 52, 6654–6663.
Poster presentation - P116
Coordination Chemistry of Selenium- and Tellurium-Containing
Pincer Ligands
Bronte J. Charette, Irit Shoichet, Jamie S. Ritch*
j.ritch@uwinnipeg.ca
Department of Chemistry, The University of Winnipeg
515 Portage Avenue, Winnipeg, Manitoba, R3B 2E9, Canada
Selenium and tellurium have widespread applications in materials chemistry, for
instance in photovoltaic[1] and thermoelectric[2] materials. Compared to the use of
organophosphines, however, the use of organochalcogen groups in ligands for
coordination chemistry and catalytic applications remains relatively unexplored.
Recent studies have shown such systems show great promise for promoting carboncarbon bond forming reactions with high efficiency, even exceeding the performance
of phosphine-based systems in some cases.[3] To expand the structural variety of
known heavy chalcogen pincers and establish structure-activity relationships, we are
pursuing several new ligand motifs. This presentation will outline the synthesis and dblock coordination chemistry of new pincer-type ligands (Figure 1) featuring amido
or carbene donors, flanked by organoselenium or tellurium groups.
Figure 1: Se,C,Se and Se,N,Se pincer ligands.
Acknowledgements: Financial support from the University of Winnipeg is gratefully acknowledged.
References:
[1] R. W. Birkmire, B. E. McCandless, Curr. Opin. Solid State Mater. Sci., 2010, 14, 139-142.
[2] B. Poudel, Q. Hao, Y. Ma, Y. C. Lan, A. Minnich, B. Yu, X. A. Yan, D. Z. Wang, A. Muto, D.
Vashaee, X. Y. Chen, J. M. Liu, M. S. Dresselhaus, G. Chen, Z. F. Ren, Science, 2008, 320, 634-638.
[3] A. Kumar, G. K. Rao, A. K. Singh, RSC Adv., 2012, 2, 12552-12574.
Poster presentation - P117
Novel reaction of 1,2,5-chalcogenadiazoles – coordination of anions
by chalcogen atoms
Nikolay A. Semenov* , Elizaveta A. Suturina, Nikolay A. Pushkarevsky, Anton.V.
Lonchakov, Irina Yu. Bagryanskaya, Enno Lork, Nina P. Gritsan, Jens Beckmann,
Andrey V. Zibarev
klaus@nioch.nsc.ru
Institute of Organic Chemistry, Russian Academy of Science
Lavrentiev Ave 9, 630090 Novosibirsk, Russia
It was recently found that 3,4-dicyano-1,2,5-chalcogenadiazoles possessing heavier
chalcogens 1 and 2 interact with certain anions (X–) to form stable anionic complexes,
in which X– are coordinated by chalcogen atom of heterocycle.[1] This contribution
covers synthetic, structural and thermodynamic aspects of this novel reaction. All
prepared complexes are characterized by single-crystal X-ray diffraction, ESI-MS,
electronic absorption spectroscopy, as well as analyzed by means of DFT
calculations. In all studied cases interaction may be described as donor-acceptor one –
chemical bond between initial components is formed via negative hyperconjugation,
i.e. electron density transfer from lone-pair orbital of X– onto the virtual σ -orbital of
the E-N bond of chalcogenadiazole. Thus, this reaction is potentially of a general
character and new objects – heterocycles, including 1,2,5-thiadiazoles, and anions
may be involved.
Figure 1. Interaction of 3,4-dicyano-1,2,5-chalcogendiazoles with anions (left). X-Ray
structure of the salt [K(18-crown-6)]+[2-SPh]- (right).
Acknowledgements: The authors are grateful to the Russian Foundation for Basic Research (project
14-03-31653) and Deutsche Forschungsgemeinschaft (project BE 3716/3-1) for the financial support.
References:
[1] N. A. Semenov, A. V. Lonchakov, N. A. Pushkarevsky, E. A. Suturina, V. V. Korolev, E. Lork, V.
G. Vasiliev, S. N. Konchenko, J. Beckmann, N. P. Gritsan, A. V. Zibarev, Organometallics 2014, 33,
4302-4314.
Poster presentation - P118
PCP-Bridged, Chalcogen-Centered Ligands: Coordination
Chemistry and Redox Transformations
Jari Konu,*(a) Ian S. Morgan,(a) Heikki M. Tuononen,(a) Tracey L. Roemmele,(b)
René T. Boeré,(b) Tristram Chivers
jari.a.konu@jyu.fi
(a) Department of Chemistry, University of Jyväskylä
P.O.Box 35, FI-40014, Jyväskylä, Finland
(b) Department of Chemistry and Biochemistry, University of Lethbridge
(c) Department of Chemistry, University of Calgary, Calgary, AB, Canada T2N 1N4
The versatile coordination and redox behaviour of the multidentate, PCP-bridged
ligands 1 and 2, as well as their carbon based reactivity, has been recently established
through various examples from main group and transition metal compounds.[1] This
family of chalcogen-centered ligands has now been expanded with trichalcogeno
monoanion 3, which displays a four-coordinate central PCP-carbon atom in contrast
to the three-coordinate carbon centers in dianions 1 and 2. In this contribution we will
describe the coordination behaviour of the novel ligand 3 and the redox activity of the
resulting complexes, for instance, through the first example of structurally
characterized six- and four-coordinate isomers of a Ni(II) complex with the same
ligand (in 4a and 4b).
Figure 1. PCP-bridged, chalcogen-centered ligands and structural isomerism in the
homoleptic Nickel(II) complex.
Acknowledgements: Financial support from the University of Jyväskylä and the Natural Sciences and
Engineering Council (Canada) is gratefully acknowledged.
References:
[1] (a) T. Chivers, J. Konu, R. Thirumoorthi, Dalton Trans., 2012, 41, 4283 (review); (b) J. Konu, T.
Chivers, H. M. Tuononen, Chem. Eur. J., 2011, 17, 11844; (c) J. Konu, T. Chivers, H. M. Tuononen,
Chem. Eur. J., 2010, 16, 12977.
Poster presentation - P119
Ferrocenyl Substituted 1,3-Dithiolanes via [3+2]-Cycloadditions of
Thiocarbonyl S-Methanides with Ferrocenyl/Hetaryl Thioketones
Grzegorz Mlostoń*, Róża Hamera
gmloston@uni.lodz.pl
epartment of rganic & Applied Chemistry, University of Łódź
Department of Organic & Applied Chemistry, University of Łódź, PL-91-403 Łódź,
Tamka 12, Poland
Thioketones form a group of reactive dieno- and dipolarophiles, which are considered
as versatile building blocks, useful for the preparation of sulfur heterocycles with
variable ring size.[1] Ferrocenyl substituted sulfur heterocycles are of great
importance.[2] Although the synthesis of diferrocenyl thioketone[3] was reported some
time ago, the non-symmetrical, ferrocenyl functionalized thioketones are unknown. In
our hands, thionation of ferrocenyl/hetaryl ketones using Lawesson’s Reagent opens a
straightforward access to synthetically attractive ferrocenyl/hetaryl thioketones 1. In
the course of our ongoing studies on the reactions of the C=S compounds with
thiocarbonyl ylides 2, reactions of selected tioketones 1 with the in situ generated
thiocarbonyl S-methanides were performed in THF solution. The 1H and 13C NMR
analyses of crude reaction mixtures proved that the reactions occurred regioselectively
and led to sterically crowded 1,3-dithiolanes 4 as sole or major products. In
communication, the stepwise mechanism of a diradical [3+2]-cycloaddition via
mesomeric stabilized 1,5-diradical 3 as a key intermediate,[4] will be discussed.
Acknowledgements: The authors thank the National Science Center (Cracow, Poland) for financial
support within the grant Maestro (Grant Maestro-3 (Dec-2012/06/A/ST5/00219)
References:
[1] G. Mlostoń, H. Heimgartner, H. In Targets in Heterocyclic Systems, 10, Attanasi, O. A.; Spinelli,
D. (Eds.); Società Chimica Italiana: Roma, 2006; 266–300.
[2] . owalski, R. arpowicz, G. Mlostoń, D. Miesel, A. Hildebrandt, H. ang, R. Czerwoniec, B.
Therrien, Dalton Transactions, 2015, 44, 6268.
[3] M. Sato, M. Asai, J. Organomet. Chem. 1992, 430, 105.
[ ] G. Mlostoń, P. Pipiak. A. Linden, H. Heimgartner, Helv. Chim. Acta, 2015, 98, DOI:
10.1002/hlca.201500057
Poster presentation - P120
Synthesis and biological evaluation of new 5-aryl-4,5-dihydro-1,3,4thiadiazole analogues as small molecule antimicrobial agents
Mansura Akter, Rainer Streubel
rupajnu@yahoo.com
Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn
Gerhardt-Domagk-Str. 1, GER-53121 Bonn
Aryl-1,3,4-thiadiazoles compounds have received considerable interest in the last
years due to having their broad spectrum of biological activity.[1,2] The synthesis of a
series of new 5-aryl-4,5-dihydro-1,3,4-thiadiazole analogues were carried out
according to the procedure[3] described in figure 1. In the first step, the intermediate
aryli-denethiosemicarbazone analogues 1-10 were prepared via condensation reaction
of thiosemicarbazide and benzaldehyde derivatives in ethanol; upon cyclization with
acetic anhydride 2,4-diacylated 5-aryl-1,3,4-thiadiazole analogues 11-20 were
obtained.[4] The structures of the synthesized compounds were elucidated by using IR,
1
H NMR spectroscopic and mass spectrometric data. The antibacterial activities of the
synthesized thiadiazole analogues were determined and most of the synthesized
compounds showed notable antibacterial activities against both the Gram-positive and
Gram-negative bacteria.
Figure 1: Synthesis of 5-phenyl- 4, 5-dihydro-1,3,4-thiadiazole analogues.
References:
[1] Alam M. S., Liu L., Lee D. U., Chem. Pharm. Bull., 2011, 59, 1413.
[2] a) Demirbas A., Sahin D., Demirbas N., Karaoglu S. A., Eur. J. Med. Chem., 2009,44, 2896—2903.
b) Kumar D., Maruthi Kumar N., Chang K.-H., Shah K., Eur. J. Med. Chem., 2010,45, 4664—4668. c)
Michael R., Stillings M. R., Welbourn A. P., Walter D. S., J. Med. Chem.,1986, 29, 2280—2284.
[3] Kubota S., Ueda Y., Fujikane K., Toyooka F., Shibuya M., J. Org. Chem.,1980, 45, 1473—1477.
[4] Akter M., Alam M. S., to be published.
Poster presentation - P121
In Search of Heavy Chalcogenido-d10-metallates
Carsten Donsbach, Stefanie Dehnen*
donsbach@students.uni-marburg.de
Department of Chemistry, Philipps-University of Marburg
Hans-Meerwein-Strasse 4, D-35032 Marburg
Chalcogenidometallate compounds provide a variety in both structural and chemical
properties while accessible via different synthetic pathways. Those include solid state
as well as solvothermal and solution reactions. Solvothermal methods have been
extended to the use of ionic liquids as solvent. Due to the interesting dissolving
characteristics of ionic liquids (de-)construction and transformation of
chalcogenidotetrelate frameworks are achieved by ionothermal treatment of binary
precursors controlled by variation of solvent, temperature and additives.[1] Research in
the field of semiconductor materials is also interested in heavy
chalcogenidometallates and their photoelectrical and thermoelectrical properties.
Synthesis via solid state and aminothermal reactions lead to potential precursor
compounds for ionothermal treatment such as K2Hg3Se4, K2Hg2Se3 and
K4PbSe4∙en∙NH3.[2] Current investigations are expanded from chalcogenidomercurates
towards –thallates, –plumbates and –bismutates, using new ionic liquids.
Figure 1. Synthetic strategy towards chalcogenidometallate compounds.
Acknowledgements: This work is supported by Deutsche Forschungsgemeinschaft (DFG) within the
framework of SPP 1708.
References:
[1] Y. Lin, D. Xie, W. Massa, L. Mayrhofer, S. Lippert, B. Evers, A. Chernikov, M. Koch, S. Dehnen,
Chem. Eur. J. 2013, 19, 8806-8813.
[2] (a) M. G. Kanatzidis, Y. Park, Chem. Mat. 1990, 2, 99-101. (b) G. Thiele, S. Lippert, F.
Fahrnbauer, P. Bron, O. Oeckler, A. Rahimi-Iman, M. Koch, B. Roling, S. Dehnen, 2015, submitted.
(c) G. Thiele, T. Krüger, S. Dehnen, Angew. Chem. 2014, 126, 4787-4791.
Poster presentation - P122
Ionothermal Treatment of Chalcogenidometallates
Silke Santner, Stefanie Dehnen*
santners@students.uni-marburg.de
Department of Chemistry, Philipps-Universität Marburg
Hans-Meerwein-Strasse 4, D-35032 Marburg
Open-framework chalcogenidotetrelates combine the advantages of zeolite-like
structures with the physical and chemical properties of chalcogenides. Besides their
formation in protic solvents, or by hydrothermal/solvothermal approaches,
ionothermal reactions have recently received increasing attention.[1] In a bottom-up
strategy, ionothermal reactions of binary or ternary precursors, such as [TSe4]4–,
[T4Se10]4– (T = Ge, Sn) or [M4Sn4Se17]10– (M = Mn, Zn, Cd), with or without
additional metal salts or amines were carried out. This yielded frameworks like 3D{[Sn9Se20]4–}[2] (1), the layered anionic structure 2D-{[Sn3Se7]2-}[3] (2), stabilized by
in-situ formed [Mn(en)2.5(en-Me0)0.5]2+ ions,[4] or the molecular „zeoball“ anion
[Sn36Ge24Se132]24–[5] (3) with spherical shape and a large cavity, being the largest main
group element cluster anion known to date. By extending these synthetic strategies to
further ionic liquid combinations or elemental compositions, including other metals as
well as other chalcogenides, new interesting structures and properties are expected.
Figure 1. Ionothermal treatment of binary and ternary chalcogenidotetrelates in ionic liquids
yields a 3D-framework (1), 0D-cluster anions (3) or a 2D-layered structure (2).
Acknowledgements: This work was supported by the Deutsche Forschungsgemeinschaft within the
frameworks of SPP 1415 and SPP 1708.
References:
[1] (a) J. Heine, S. Dehnen, Z. Anorg. Allg. Chem. 2012, 638, 2425; (b) T. Wu, X. Wang, X. Bu, X.
Zhao, P. Feng, Angew. Chem. 2009, 121, 7340.
[2] Y. Lin, S. Dehnen, Inorg. Chem. 2011, 50, 7913.
[3] G. Xu, C. Wang, P. Guo, Acta Crystallogr. 2009, C65, m171.
[4] S. Santner, S. Dehnen, Inorg. Chem. 2015, 54, 1188-1190.
[5] Y. Lin, W. Massa, S. Dehnen, J. Am. Chem. Soc. 2012, 134, 4497.
Poster presentation - P123
Probing Donor-Acceptor Interactions in peri-Substituted
Diphenylphosphinoacenaphthyl-Element Dichlorides of Group 13 &
15 Elements
Emanuel Hupf, Enno Lork, Stefan Mebs, Lilianna Chęcińska, Jens Beckmann
hupf@uni-bremen.com
Institut für Anorganische Chemie, Universität Bremen
Leobener Str, GER-28359, Bremen
The reaction of ArLi with ECl3 (E = Al, P, In, Bi) and ArSnBu3 with ECl3 (E = B, Ga,
Tl, Sb, Bi) proceeds via transmetallation reaction to give the
diphenyl-phosphino-acenaphthyl-element dichlorides ArECl2 (Ar = 6-Ph2P-Ace-5-).
The structural elucidation by single-crystal X-ray diffraction and DFT calculations
showed that compounds of the series ArECl2adopt three different structure types (see
Figure 1). All compounds of group 13 elements show a distorted tetrahedral
arrangement at the triele atom and short P-E peri-distances, indicating attractive
interactions between P and E (structure type A). Within the series of group 15
compounds two distinct structure types are observed depending on the environment.
For ArECl2containing the elements P, As and Bi a T-shaped spatial arrangement with
a nearly linear Cl-E-Cl linkage and short P-E peri distances are observed (type B). In
contrast, ArSbCl2 shows a nearly rectangular Cl-E-Cl linkage with a long P-Sb peridistance, which is associated with repulsive interactions (type C).[1]
Figure 1. Different structure types within the series of compounds ArECl2.
References:
[1] E. Hupf, E. ork, S. Mebs, . Chęcińska, J. Beckmann, Organometallics, 2014, 33, 7247.
Poster presentation - P124
Straightforward formation of the unprecedented 5-membered
annulated ring containing the B-N moiety: 1H-2,1-benzazaborolyl
alkali metal salts, reactivity with electrophiles and redox behavior
Martin Hejda, Roman Jambor, Aleš Růžička, Antonín yčka and ibor Dostál
martin.hejda@student.upce.cz
Department of General and Inorganic Chemistry, Faculty of Chemical Technology,
University of Pardubice
Studentská 573, CZ - 532 10, Pardubice, Czech Republic
1,2-azaborolyl anion is known in the literature for a long time and already has been
used as ligand for both transition and main group metals as cyclopentadienyl class
ligand analogues.[i,ii] However, there are no reports dealing with analogous
benzannulated 1H-2,1-benzazaboroles (Fig. 1C) in this respect. Recently, we have
found,[iii] that reduction of variously substituted C,N-chelated chloroboranes (Fig. 1A)
with potassium metal afforded various derivatives of symmetric (3,3’)-bis(1H-2,1benzazaborole) (Fig. 1B). Subsequent reduction of these compounds with two
equivalents of alkali metal (M = Li, Na or K) proceeds via unique reaction pathway
and produced the first 1H-2,1-benzazaborolyl (Bab) alkali metal salts M+(THF)(Bab)(Fig. 1C). These salts are extremely strong reducing agents. Nevertherless, they are
still able to react with simple electrophiles under formation of substituted 1H-2,1benzazaboroles, but they also convert with starting C,N-chelated chloroboranes to
unsymmetrically substituted (3,3’)-bis(1H-2,1-benzazaborole), thereby opening a new
strategy for preparation of such C-C bridged heterocyclic systems. Reaction
mechanisms, molecular structures, some experimental data and the latest results will
be reported.
Figure 1.
Acknowledgements: The authors wish to thank the Grant Agency of the Czech Republic project No.
P207/12/0223.
References:
[i] (a) G. Schmid, Comments Inorg. Chem., 1985, 4, 17-32. (b) S.-Y. Liu, M.-C. Lo, G. C. Fu, Angew.
Chem. Int. Ed., 2002, 41, 174-176.
[ii] For example see: A. J. Ashe III, Organometallics, 2009, 28, 4236-4248.
[iii] M. Hejda, R. Jambor, A. Růžička, A. yčka, . Dostál, Dalton Trans. 2014, 43, 9012-9015.
Poster presentation - P125
Catalytic Dehydrogenation of Amino Boranes – Formation of
Condensed Borazine Compounds
Fabian Müller, Monica Trincado, and Hansjörg Grützmacher*
fmueller@inorg.chem.ethz.ch
Laboratory of Inorganic Chemistry, Department of Chemistry and Applied
Biosciences, ETH Zurich
Vladimir-Prelog-Weg 1, 8093 Zurich, Switzerland
Amino boranes are studied as fuels with respect to hydrogen storage and as precursors
for inorganic materials. Thermal decomposition leads to polymeric BN compounds in
form of nanotubes, nanoparticles or clusters.[1] With a new Ru diazadiene diolefin
complex we achieved the synthesis of condensed borazine compounds (Figure 1).
Remarkably, these poly(borazines) are soluble and contain likely polycondensed rings
up to B50N49H28 and only little insoluble polymeric material is formed.[2]
Figure 1. Reaction equation of dehydrogenation of amino boranes.
References:
[1] U. Kusari, Z. Bao, Y. Cai, G. Ahmad, K. H. Sandhage, L. G. Sneddon, Chem. Commun. 2007,
1177–1179.
[2] M. Trincado, H. Grützmacher, Unpublished Results, 2015.
Poster presentation - P126
Titanocene-based Catalysts for Amine Borane Dehydrocoupling:
Studies of the Mechanistic Role of Ti(III) Species and Formation of
Polyaminoboranes
Titel Jurca, Ian Manners*
titel.jurca@bristol.ac.uk
School of Chemistry,
University of Bristol Cantock’s Close, BS8 1TS, Bristol, UK
Catalytic dehydrocoupling/dehydrogenation of amine-boranes has become a field of
intense interest and rapid growth; largely driven by potential applications in hydrogen
storage, transfer hydrogenations, and synthesis of novel inorganic polymers.
Consequently, a wide variety of catalyst systems have been developed to promote this
reaction, with the majority based on rare and expensive late transition metals.[1] Our
group has previously reported that Group 4 metallocene [Cp2Ti] is an efficient
homogeneous catalyst for the dehydrogenation of secondary amine-borane adducts
R2NH·BH3 (R = Me, iPr). Prior mechanistic understanding of this reaction centered
around the interplay of Ti intermediates in the +2 and +4 oxidation states.[2] Our
group had previously reported the isolation of paramagnetic Ti III species as potential
intermediates in the catalytic dehydrogenation process.[3] We report the synthesis of
several new TiIII species, and their catalytic activity for the dehydrocoupling of
secondary amine-boranes. Our results reinforce that paramagnetic TiIII species play a
role in the dehydrogenation chemistry. Moreover, we have recently found that
modifications to the ligand framework can have drastic effects on catalyst
performance. For example, several new variants of our titanocene-based catalysts
display not only a ten-fold increase in activity for the dehydrocoupling of secondary
amine-boranes, but are also active as dehydropolymerization catalysts for primary
amine-boranes; the first example of early transition metal amine-borane
polymerization catalysts.
Acknowledgements: Naomi Stubbs, Dr. George R. Whittell, Dr. Erin M. Leitao.
References:
[1] E. M. Leitao, T. Jurca, I. Manners, I. Nature Chem. 2013, 5, 817-829.
[2] (a) T. J. Clark, C. A. Russell, I. Manners, J. Am. Chem. Soc. 2006, 128, 9582-9583. (b) M. E. Sloan,
A. Staubitz, T. J. Clark, C. A. Russell, G. C. Lloyd-Jones, I. Manners, I. J. Am. Chem. Soc. 2010, 132,
3831-3841.
[3] H. Helten, B. Dutta, J. R. Vance, M. E. Sloan, M. F. Haddow, S. Sproules, D. Collison, G. R.
Whittell, G. C. Lloyd-Jones, I. Manners, Angew. Chem. Int. Ed. 2013, 52, 437-440.
Poster presentation - P127
1,2-Azaborine, the BN derivative of ortho-benzyne
Klara Edel,(a) Sarah A. Brough,(a) Ashley N. Lamm,(b) Shih-Yuan Liu,b,c Holger F.
Bettingera,*
klara.edel@uni-tuebingen.de
Institut für Organische Chemie, Universität Tübingen
(a)Auf der Morgenstelle 18, 72076 Tübingen, Germany, (b) Department of Chemistry
and Biochemistry, University of Oregon, Eugene, Oregon 97403-1253, United States,
(c) Department of Chemistry, Boston College, Chestnut Hill
Ortho-benzyne 1 is a well-known and extremely useful reactive intermediate in
organic chemistry. The formal substitution of the CC-triple bond by an isoelectronic
BN bond relates 1 to the azaborine 2. Here we show by direct spectroscopic
techniques that 1,2-azaborine can exist as reactive intermediate. We found that 2 can
be generated by flash vacuum pyrolysis (FVP) from precursor 3 by thermal
elimination of t-butyldimethylsilylchloride (TBSCl) and isolated in cryogenic
matrices. 1,2-Azaborine spontaneously binds dinitrogen N2 (adduct 4) in a
photochemically reversible transformation.
Figure 1. Generation of 1,2-azaborine (2) by FVP of 3 and trapping with N2.
Acknowledgements: The research was supported by the Deutsche Forschungsgemeinschaft and the
National Institutes of Health (Grant R01-GM094541).
References:
[1] For selected reviews on aryne chemistry, see: (a) C. M. Gampe and E. M. Carreira, Angew. Chem.,
Int. Ed. Engl., 2012, 51, 3766-3778; (b) P. M. Tadross and B. M. Stoltz, Chem. Rev., 2012, 112, 35503577; (c) H. Yoshida and K. Takaki, Synlett, 2012, 23, 1725-1732; (d) A. Bhunia, S. R. Yetra and A. T.
Biju, Chem. Soc. Rev., 2012, 41, 3140-3152; (e) C. Wentrup, Aust. J. Chem., 2010, 63, 979-986; (f) T.
Kitamura, Aust. J. Chem., 2010, 63, 987-1001; (g) H. H. Wenk, M. Winkler and W. Sander, Angew.
Chem., Int. Ed. Engl., 2003, 42, 502-528; (g) H. Pellissier and M. Santelli, Tetrahedron, 2003, 59, 701730.
Poster presentation - P128
Fragmentation vs. Dehydogenation of Borazines
Peter Grüninger, Holger F. Bettinger*
p.grueninger@student.uni-tuebingen.de
Institut für Organische Chemie, Universität Tübingen
Auf der Morgenstelle 18, 72076 Tübingen, Germany
A well-known concept to manipulate the electronic properties of polycyclic aromatic
hydrocarbons, nanographenes, and possibly graphene is the isoelectronic substitution
of CC by BN units.[1] Our interest is the flash vacuum pyrolysis (FVP) and
photochemistry of borazine containing aromatic compounds, such as 1-3. We
investigate competition of the dehydrogenation (path I) and fragmentation (path II)
into reactive molecules using matrix isolation techniques.
Figure 1. Borazine containing aromatic compounds 1-3 and possible reactions,
dehydrogenation (path I) to BN-HBC (5) and cycloreversion (path II) to dibenz[c,e][1,2]azaborine (4), exemplified for 3.
Acknowledgements: This research was supported by the Deutsche Forschungsgemeinschaft.
References:
[1] (a) M. J. D. Bosdet, W. E. Piers, Can. J. Chem., 2009, 87, 8; (b) P. G. Campbell, A. J. V. Marwitz,
S.-Y. Liu, Angew. Chem. Int. Ed., 2012, 51, 6074; (c) S.-M. Jung, E. K. Lee, M. Choi, D. Shin, I.-Y.
Jeon, J.-M. Seo, H. Y. Jeong, N. Park, J. H. Oh, J.-B. Baek, Angew. Chem. Int. Ed.,2014, 53, 2398; (d)
X.-Y. Wang, F.-D. Zhuang, X.-C. Wang, X.-Y. Cao, J.-Y. Wang, J. Pei, Chem. Commun.,2015, 51,
4368; (e) X.-Y. Wang, J.-Y. Wang, J. Pei, Chem. Eur. J.,2015, 21, 3528; (f) M. Müller, S. Behnle, C.
Maichle-Mössmer, H. F. Bettinger, Chem. Commun., 2014, 50, 7821.
Poster presentation - P129
Cationic and Anionic Chains of only Lewis Base Stabilised
Pnictogenylboranes
Christian Marquardt, Manfred Scheer*
christian.marquardt@ur.de
Institute of Inorganic Chemistry, University of Regensburg
Universitätsstraße 31, GER-93053, Regensburg
In the recent years the interest in the chemistry of compounds containing Group 13/15
elements increased considerably. Especially the borane adducts of nitrogen-donors
containing a high percentage of hydrogen are intensively discussed as new hydrogenstorage materials.[1] Surprisingly, borane adducts of phosphorus-donors or even
heavier analogs have not been studied thoroughly yet. Recently, we reported about a
new and convenient way to synthesize the parent and mixed substituted
pnictogenylboranes, which were not accessible by previously published methods.[2]
The pnictogenylboranes “H2EBH2·NMe3” (E = P, As) serve as readily available
building blocks for mixed Group 13/15 element cationic chains.[3] In addition, first
examples of anionic species have also been obtained. These unprecedented molecules
show a rich subsequent chemistry, including the formation of extended chain
molecules. Furthermore they can be used for the synthesis of inorganic polymers, or
as precursors for 13/15 composite materials.
Figure 1. Selected pnictogenylborane chains.
Acknowledgements: DFG and COST action CM1302 are gratefully acknowledged.
References:
[1] A. Staubitz, A. P. M. Robertson, I. Manners, Chem. Rev. 2010, 110, 4023.
[2] C. Marquardt, A. Adolf, A. Stauber, M. Bodensteiner, A.V. Virovets, A. Y. Timoshkin, M. Scheer,
Chem. Eur. J. 2013, 19, 11887.
[3] C. Marquardt, C. Thoms, A. Stauber, G. Balázs, M. Bodensteiner, M. Scheer, Angew. Chem. Int.
Ed. 2014, 53, 3727.
Poster presentation - P130
Cooperative Al/P Lewis Pairs Based on Cationic Aluminium
Complexes
Tom Stennett, Jürgen Pahl, Sjoerd Harder*
tom.stennett@fau.de
Institut für Anorganische Chemie, Friedrich-Alexander-Universität Erlangen
Nürnberg
Egerlandstraße 1 91058 Erlangen Germany
The unquenched interaction of Lewis acids and bases that cannot form adducts due to
steric repulsion was introduced in 2006 as a concept for stoichiometric and catalytic
transformations of small molecules.[1] Recently, this approach has been extended to
acid/base pairs that, despite reduced steric encumbrance, do not interact strongly due
to poor orbital overlap and/or mismatched polarizability.[2] Cationic, coordinatively
unsaturated aluminium complexes, [NacnacAlMe][B(C6F5)4] (Nacnac = βdiketiminate) undergo intramolecular reactions with alkenes,[3] alkynes, CO2 and
epoxides. However, these reactions tend to have unstable products and involve ligand
non-innocence. Addition of a phosphine to such cationic complexes results in varying
degrees of Al-P interaction, depending on the phosphine employed. Systems based on
PPh3, PtBu3 and a phosphine-substituted β-diketiminate provide a wide range of
frustrated Lewis pair type reactivity at the metal centre, including the binding of
unsaturated small molecules and the catalytic dehydrocoupling of Me2NH-BH3.
Figure 1. Small molecule activation with a cooperative Al+/P pair.
References:
[1] G. C. Welch, R. R. San Juan, J. D. Masuda, D. W. Stephan, Science 2006, 314, 1124–1126.
[2] S. Roters, C. Appelt, H. Westenberg, A. Hepp, J. C. Slootweg, K. Lammertsma, W. Uhl, Dalton
Trans. 2012, 41, 9033.
[3] C. E. Radzewich, M. P. Coles, R. F. Jordan, J. Am. Chem. Soc. 1998, 120, 9384.
Poster presentation - P131
Binary Group 13/14 and 13/15 Zintl Anions and Their Reactions
towards Ternary Intermetalloid Clusters
Niels Lichtenberger, Stefanie Dehnen*
niels.lichtenberger@chemie.uni-marburg.de
Department of Chemisty, Philipps University of Marburg
Hans-Meerwein-Straße, GER-35043, Marburg
Intermetalloid clusters that combine main group (semi-)metals with transition metals
belong to the most recent developments in the field of Zintl anion chemistry,
attracting both chemists and physicists due to their unique structural and electronic
properties.[1] Recently, we were able to extend the field to the use of small binary
anions comprising triel elements (TrBi3)2– (Tr = Ga, In), which have proven to be
powerful synthetic building blocks for new polyanionic clusters.[2] Our results led us
to investigate the chemistry of the binary Zintl anions with the heaviest triel metal
thallium. Thereby, we were able to isolate a variety of new anions and gain more
insight into the influence of the triel element on reaction products and relative
stabilities. Furthermore, new and unprecedented intermetalloid clusters with
intriguing electronic and structural properties were obtained. To enable a better
understanding of the bonding situations and to allow for reliable atom assignments we
employed quantum chemical methods
Figure 1. Intermetalloid cluster anions K2[Tl@Tl7Pb5]4– (left) and [Bi6-(µ3-Zn)3-Bi5Tl]4–
(right).
References:
[1] S. Scharfe, F. Kraus, S. Stegmaier, A. Schier, T. F. Fässler, Angew. Chem. Int. Ed. 2011, 50, 3630.
[2] a) B. Weinert, F. Weigend, S. Dehnen, Chem. Eur. J. 2012, 18, 13589; b) B. Weinert, A.R.
Eulenstein, R. Ababei, S. Dehnen, Angew. Chem. Int. Ed. 2014, 53, 4704; c) B. Weinert, F. Müller, K.
Harms, R. Clérac, S. Dehnen, Angew. Chem. Int. Ed. 2014, 53, 11979-11983.
Poster presentation - P132
Toward Connection of Aromatics and Ruthenium Complexes to
Tin/Sulfur Clusters
Eliza Leusmann Stefanie Dehnen*
leusmann@staff.uni-marburg.de
Department of Chemistry, Philipps-University Marburg
Hans-Meerwein-Str. 4, 35043 Marburg, Germany
In recent years, the design of ruthenium complexes has attracted great interest due to
their properties which are useful for diverse applications like in dye-sensitized solar
cells[1], as chromophores[2] or in water oxidation[3]. Many of these complexes include
N-donor, chelating ligands like terpyridines.[1] In our group, we have developed the
ligands of organotetrelchalcogenide cages, especially a double-decker-like RSn/S
cluster based on an inorganic Sn4S6 core. Starting out from a ketofunctionalized ligand
R = CMe2CH2COMe, reactions with hydrazine derivatives have been successful. To
combine the versatile properties of the inorganic cluster core with the potentially
applicable properties of Ru(II) complexes, one of our aims is to attach these to an
Sn/S cage. This can be achieved either by functionalization of the Sn/S cluster with a
suitable donor ligand and subsequent Ru(II)-semisequestration or by attachment of a
pre-formed Ru(II) complex to the cluster - like connection of acetylruthenocene[5].
Newest research shows that attachment of chelating ligands to the Sn/S cluster is
possible, e.g. bipyridine and chinoline.[6]
Figure 1. Molecular structure of the ruthenocenyl-decorated Sn/S cluster.
Acknowledgements: We thank the DFG-GRK 1782 for financial support.
References:
[1] P. G. Bomben, T. J. Gordon, E. Schott, C. P. Berlinguette, Angew. Chem. 2011, 123, 10870-10873.
[2] K. C. D. Robson, C. P. Berlinguette et al., Inorg. Chem. 2011, 50, 5494-5508.
[3] B. Radaram, X. Zhao et al., Inorg. Chem. 2011, 50, 10564-10571.
[4] Z. Hassanzadeh Fard, L. Xiong, C. Müller, M. Holynska, S. Dehnen, Chem. Eur. J. 2009, 15, 65956604.
[5] E. Leusmann, M. Wagner, N. W. Rosemann, S. Chatterjee, S. Dehnen, Inorg. Chem. 2014, 53,
4228-4233.
[6] E. Leusmann, F. Schneck, S. Dehnen, submitted.
Poster presentation - P133
Ag(I) Coordination Polymers of Cyclophosphazenes
Derya Davarc , unus Zorlu, Rüştü Gür, Serap Beşli
ddavarci@gtu.edu.tr
Department of Chemistry
Gebze Technical University, 41400, Kocaeli, Turkey.
Hexachlorocyclotriphosphazene (trimer) and octachlorocyclotetraphosphazene
(tetramer) which are inorganic heterocyclic rings have used in many studies because
of having reactive P-Cl bounds. Cyclophosphazene compounds are capable to bind
metal ions through endocyclic and exocyclic ring nitrogen atoms. Especially, trimer
derivatives containing pyridyloxy groups have used as ligand in the literature [1-4]. In
this study we have synthesized new silver (I) coordination polymers by using trimer
and tetramer ligands. We have targeted to obtain metal organic framework of these
coordination compounds and to focus on the effect of ring size and number of donor
atoms on crystal structures.
Figure 1. Crystal structures of Ag(I) coordination polymers (a) trimer and (b) tetramer.
Acknowledgements: The authors would like to thank the Scientific and Technical Research Council of
Turkey for financial support (grant 114Z566)
References:
[1] V. Chandrasekhar, R. S. Narayanan, Dalton Trans., 2013, 42, 6619-6632.
[2] E. W. Ainscough, A. M. Brodie, R. J. Davidson, C. A. Otter, Inorg. Chem. Commun., 2008, 11,
171–174 .
[3] E. W. Ainscough, A. M. Brodie, P.J.B. Edwards, G.B. Jameson, C. A. Otter, S. Kirk, Inorg. Chem.,
2012, 51, 10884-10892.
[4] E. W. Ainscough, A. M. Brodie, C. V. Depree, A. Derwahl, B. Moubaraki, K. S. Murry, C. A.
Otter, Dalton Trans., 2005, 3337-3343.
Poster presentation - P134
Chiral Oxazoline Complexes of Basal Bulky Cobalt Sandwich
Compounds and Cyclophosphazenes
Jatinder Singh, Dheeraj Kumar and Anil J. Elias*
jatinder.iitd@gmail.com
Department of chemistry, IIT Delhi
Hauz Khas, New Delhi-110016
Among metal sandwich compounds, one of the best competitors for ferrocene with
regard to stability, ease of synthesis and reaction chemistry is the 18 electron cobalt
sandwich compound [(η5-Cp)Co(η4-C4Ph4)]. While the molecule as such is much less
reactive than ferrocene, its cyclopentadienyl derivatives, especially the carboxylate
ester has shown excellent potential for developing novel chiral organometallic
catalysts
for
asymmetric
synthesis
ably
assisted
by
the
bulky
tetraphenylcyclobutadiene moiety. Monomeric and dimeric palladacycles based on
(η5-Cp)Co(η4-C4Ph4) and [(η5-Cp)Co(η4-C4Ph3)]2 are well documented with
established utility in homogeneous asymmetric catalysis. However, all these cobalt
sandwich based palladacycles have the chiral binding moiety positioned on the
cyclopentadienyl ring and the palladacycles were formed from a C-H activation
followed by cyclopalladation of the cyclopentadienyl bound protons. Six membered
cyclophosphazene ring can also act as an excellent precursor for preparing
multioxazoline ligands having C2 and C3 axis, which can play a critical role in
determining the enantioselectivity of a catalytic reaction In this presentation, we
report the synthesis and structural characterization of the first examples of a new type
of [(η5-RCp)Co(η4-C4Ph3R')] type bisoxazoline having chiral oxazolinyl units on both
the cyclobutadiene and cyclopentadienyl rings of the cobalt sandwich compound and
the first examples of C2 and C3- symmetric chiral oxazoline derivatives of
cyclophosphazenes. Preliminary studies on such compounds indicated that these
ligands have the potential to form a range of transition metal based chiral catalysts.
References:
Singh, J.; Kumar, D.; Singh, N.; Elias, A. J., Organometallics, 2014, 33, 1044-1052.
Kumar, D.; Singh, J.; Elias, A. J. Dalton Trans. 2014, 40, 4882-4891.
Poster presentation - P135
Luminescent complexes of copper(I) halides with functionalized
tertiary phosphines
Peter Bartos, Petr Taborsky, Marek Necas
barthes@mail.muni.cz
Department of Chemistry, Faculty of Science, Masaryk University
Kotlarska 2, CZ-61137, Brno, Czech Republic
Depending on copper(I) halide, ligand to metal ratio and reaction conditions,
complexes with various central CuX clusters can be prepared. Compounds containing
central Cu4(μ3-I)4cubane-like clusters in their structures have been intensively studied
because of their thermochromic behavior.[1] A series of reactions of copper(I) halides
with P(III)-containing ligands was carried out in different molar ratios in different
solvents, yielding new Cu(I) complexes, which were characterized by 31P NMR and
X-ray diffraction. The P(III)-containing ligands were based on tertiary phosphines
carrying at least one organic functional group (e.g. CN, COOH) on the alkyl/aryl
substituents. Luminescence in the complexes and its dependence on various
conditions (solvent, temperature) was also studied.
Acknowledgements: To Mr. Michal Babiak and CEITEC´s X-ray Diffraction and Bio-SAXS Core
Facility for X-ray measurements. European Regional Development Fund (CZ.1.05/1.1.00/02.0068).
References:
[1] (a) X.-C. Shan, F.-L. Jiang, H.-b. Zhang, X.-Y. Qian, L. Chen, M.-Y. Wu, S. A. AL-Thabaiti, M.-C.
Hong, Chem. Commun., 2013, 49, 10227; (b) X.-C. Shan, F.-L. Jiang, L. Chen, M.-Y. Wu, J. Pan, X.Y. Wan, M.-C. Hong, J. Mater. Chem. C, 2013, 1, 4339.
Poster presentation - P136
Self-Assembly of a Luminescent Thiolato-Stabilized
Hexanonacontanuclear Cuprous Wheel
C. W. Liu,* Jhih-Yu Cyue, Bing Li, Jian-Hong Liao
chenwei@mail.ndhu.edu.tw
Department of Chemistry, National Dong Hwa University
No 1, Sec. 2, Da Hseuh Rd. Hualien, Taiwan 97401
A cuprous wheel containing hexanonacontanuclear thiolate-bridged copper(I) cluster,
[Cu96{SC(O)OiPr}96] 1, was obtained through self-assembly of copper salts with
asymmetrical O-isopropyl monothiocarbonate ligand in acetone. X-ray crystalstructure analysis reveals that 1 crystallizes in the trigonal space group R(-)3 with a
protein-sized six-gear-like macrocyclic structure, which comprises 96 copper(I) ions
bridged by 96 O-isopropyl monothiocarbonate ligands. The molecule possesses a S6
axis, therefore only sixteen unique Cu(I) ions and sixteen ligands present in the
asymmetric unit and all atoms are located in general positions. The compound 1
exhibits an orange-yellow emission in the solid state at ambient temperature and at
77K upon irradiation with an UV lamp. Upon dissolving in solvents such as ethanol,
methanol, acetonitrile, and dihalomethane at 298 K, the emissive phenomena differ.
The dihalomethane solution produces a red luminescence, which is red shift of the
maximum emission by ca. 3400 cm−1 compared to luminescence of the crystalline
solid, but no emission is detected in ethanol, methanol and acetonitrile. However,
upon freezing in a liquid N2bath, all these glasses exhibit brilliant yellow luminescent,
which are blue-shift (by ca. 277−30 cm−1), and intensity increase relative to solidstate luminescence at 77 K. The luminescence feature displayed by dihalomethane
suggests that compound 1 is a potential sensor for halogenated species.
Acknowledgements: Financial Supports from Ministry of Science and Technology in Taiwan
Poster presentation - P137
Hexanuclear and Tetranuclear Titanium Organophosphonates
Formed via a Common Single-4-Ring Intermediate: Insights into
Formation Pathways
Kamna Sharma, Alok Ch. Kalita, Paul Davis and Ramaswamy Murugavel*
sharmakamna052@gmail.com
Deparment of Chemistry
Indian Institute of Technology, Bombay Powai-400076, Mumbai, Maharashtra India
Reactivity of diketonate modified titanium precursor [Ti(acac)2(OiPr)2] with tert-butyl
phosphonic acid at two different ratios of the reactants has been investigated.
Reaction of an equimolar quantities of tBuP(O)(OH)2and [Ti(acac)2(OiPr)2] in CH2Cl2
followed by crystallization in CH2Cl2yields the hexanuclear titanophosphonate cluster
[Ti6(µ-O)2(µ-tBuPO3)6(acac)6(OiPr)2] (1), presumably formed through the hydrolysis
of a symmetric intermediate [Ti6(µ-tBuPO3)6(acac)6(OiPr)6] (A) that is similar to the
D6R SBU of zeolites. Interestingly, when the same reaction has been carried out in
acetonitrile, a related but an asymmetric hexanuclear cluster [Ti6(µ-O)3(µ-tBuPO3)5(µt
BuPO3H)(acac)6(OiPr)] (2) has been isolated, which has also presumably formed
from A via 1 through further hydrolysis. Reaction of 1.5 equivalents of the
phosphonic acid with one equivalent of [Ti(acac)2(OiPr)2] in acetonitrile however
leads to the fortmation of a symmetric tetranuclear titanophosphate cluster [Ti4(µOH)2(µ-tBuPO3)4(µ-tBuPO3H)2(acac)4] (3), which is essentially a fusion product of
S4R titanium phosphonate [Ti(acac)(OiPr)(O3PtBu)]2 in the presence of excess
phosphonic acid and small quantities of adventitious water. The titanium clusters 1-3
have been characterized by analytical and spectroscopic techniques apart from single
crystal X-ray diffraction studies. The adjacent pair of titanium centers is bridged by µO2- ligands in 1 and 2 and a µ-OH‑ ligand in 3. All the three clusters are held together
by multiply bridging phosphonate ligands displaying either in [3.111] or [3.110]
binding mode. A common structural feature in all the three compounds is the presence
of Ti2O4P2 ring, which is the basic building block (S4R) that is formed in the early
stages of cluster development in these phosphonate clusters.
Acknowledgements: This work was supported by DST, New Delhi and DAE-BRNS, Mumbai. R.M.
thanks BRNS for a DAE-SRC Outstanding Investigator Award. KS thanks CSIR, New Delhi for
research scholrship.
Poster presentation - P138
Structural Characterization and Luminescence Studies of Au(I)
Complexes with PNP and PNB Based Ligand Systems
Shabana Khan
shabana@iiserpune.ac.in
Department of Chemistry, Indian Institute of Science Education and Research (IISER)
Pune
Dr. Homi Bhaba Road, Pune-411008, India
The PNP and PNB framework based gold(I) complexes have been synthesized and
studied for their structural and luminescence properties. In case of PNP based system,
reaction of corresponding L→AuCl with AgSbF6 yielded a fully supported dimeric
dinuclear Au(I) cation 1 while PNB system led the formation of dimeric mononuclear
Au(I) cation 2.[1] The molecular structure of 1 reveals the presence of a strong
intramolecular aurophilic interaction with a Au····Au bond distance of 2.758(1) Å,
one of the shortest aurophilic interactions reported in literature. However, cation 2
displays no aurophilic interaction. The effect of aurophilic interaction is also
illustrated through the study of the luminescent properties of these gold(I) complexes.
Cation 1 in which aurophilic interaction is present, exhibits blue luminescence in
solution as well as in the solid state whereas the other gold(I) complexes remain nonluminescent.
Figure 1. (a) PNP and PNB based Au(I) Cations; (b) Normalized emission spectrum and
picture of solution and solid state emission under UV light for PNP based Au(I) cation 1.
Acknowledgements: S.K. thanks SERB(India) and IISER Pune for financial support.
References:
[1] S. Pal, N. Kathewad, S. Khan (manuscript under preparation).
Poster presentation - P139
A Bimetallic Phosphorous-Based Complex as a Building Block to
Form Organometallic-Organic Hybrid Materials
Mehdi Elsayed Moussa, Bianca Attenberger, Stefan Welsch, Manfred Scheer*
mahdi.844@hotmail.fr
University of Regensburg, Institute of Inorganic chemistry
Universitatsstr. 31, GER-93053 Regensburg.
In the past thirty years research into porous materials resulted in a number of
important technological applications.[1] In this field our group is interested in the use
of organometallic complexes based on polyphosphorus ligands as bridging units
between metal centers.[2] These complexes allow the formation of one- and twodimentional polymers[3] as well as giant spherical molecules.[4] In one approach the
compound A was synthesized from the reaction between [Cp2Mo2(CO)4(η2-P2)] and
the silver salt Ag[Al{OC(CF3)3}4].[5] The reactions of A with the pyridine-based
ditopic ligands 1-4 have lead the formation of a large variety of assemblies B-F.[6]
This novel synthetic route will open up new opportunities to incorporate defined
functionalities in solid-state architectures of phosphorus ligand complexes.
Acknowledgements: The European Research Council (ERC-2013-AdG 339072) is gratefully
acknowledged for the support of this work.
References:
[1] J-R. Li, J. Sculley, H.-C. Zhou, Chem. Rev. 2012, 112, 869 (and references herein).
[2] M. Scheer, Dalton Trans, 2008, 33, 4372.
[3] J. Bai, J. V. Virovets, M. Scheer, Angew. Chem. Int. Ed. 2002, 41, 1737.
[4] J. Bai, J. V. Virovets, M. Scheer, Science, 2003, 300, 781.
[5] M. Scheer, L.J. Gregoriades, M. Zabel, et al., Chem. Eur. J. 2008, 14, 282.
[6] B. Attenberger, S. Welsch, M. Zabel, E. Peresypkina, M. Scheer, Angew. Chem. Int. Ed. 2011, 50,
11516.
Poster presentation - P140
Synthesis, crystal structure and properties of ferrocenyl based
pyridyl functionalized dithiocarbamate complexes of group 12 metals
Vinod Kumara, Michael G. B. Drewb and Nanhai Singh*
nsingbhu@gmail.com
Department of Chemistry, Banaras Hindu University
Varanasi-221005
A developing interest in the dithiocarbamate ligand chemistry is due to their
functionalization which may potentially give rise to intriguing structures and tunable
physical properties. Transition metal dithiocarbamate complexes have been
extensively studied due to their important material properties and myriad of
applications.[1-2] In this presentation new ferrocenyl based robust macrocyclic ring
metal-organic coordination polymers and dinuclear complexes involving 3- and 4pyridyl functionalized dithiocarbamate complexes of the form [M(dtc)2] (dtc =
ferrocenyl pyridin-3-ylmethyldithiocarbamate, M = Zn(II) 1, Cd(II) 2, Hg(II) 3); dtc =
ferrocenyl pyridin-4-ylmethyldithiocarbamate, M = Zn(II) 4, Cd(II) 5, Hg(II) 6)),
have been synthesized and fully characterized and their structures have been
elucidated by X-ray crystallography. Their luminescent properties and uses as single
source precursor for the preparation of mixed-metal sulphide materials are being
investigated.
Figure 1. A Zn(II) dimer and a Cd(II) polymer synthesized from the dithiocarbamate (dtc)
ligand.
Acknowledgements: Financial support from the Science and Engineering Reserach Board
(SERB,SB/S1/IC-15/2014) New Delhi, is gratefully acknowledged.
References:
[1] G. Hogarth, Prog. Inorg. Chem., 2005, 53, 71– 561.
[2] A. Kumar, R. Chauhan, K. C. Molloy, G. K. Köhn, L. Bahadur and N. Singh, Chem. – Eur. J.,
2010, 16, 4307–4314. (b) V. Singh, R. Chauhan, A. N. Gupta, V. Kumar, M. G. B. Drew, L. Bahadur
and N. Singh, Dalton Trans., 2014, 43, 4752–4761.(c) V. Kumar, V. Singh, A. N. Gupta, M. G. B.
Drew and N. Singh, Dalton Trans., 2015, 44, 1716–1723.
Poster presentation - P141
Ligand Protected Zinc Clusters
Hung Banh, Kerstin Freitag, Katharina Dilchert, Christine Schulz, Christian Gemel,
Rüdiger W. Seidel, Samia Kahlal, Jean-Yves Saillard, Roland A. Fischer*
Hung.Banh@rub.de
Chair of Inorganic Chemistry II, Ruhr-University Bochum
Universitätsstr. 150, GER-44801, Bochum
Ligand protected metal clusters [Ma]Lb linking molecular and bulk materials have
been in the focus of research for a very long time. In particular, metalloid Al and Ga
clusters (a>b) have attracted substantial interest.[1] Recently it has been predicted by
calculations that related metalloid zinc clusters have a large spectrum of electronic
properties ranging from a metallic to an insulating character, depending on the cluster
size, also exhibiting unique features, which combine both phenomena.[2] Naked zinc
clusters have been experimentally studied in the gas phase,[2] or hosted in Zeolite X[3]
or intermetallic frameworks, respectively.[4] However, ligand protected (metalloid)
clusters [Zna]Lb remained unknown, so far. Herein, we present the preparation,
structural characterization and bonding analysis of first ligand protected zinc clusters
{[Zn3]Cp*3}+ (1),[5] [Zn9]Cp*6 (2) and {[Zn10](Cp*6Me)}+ (3). The synthetic access of
these clusters is based on the reaction of [Zn2Cp*2] with [ZnCp*2] or ZnMe2 in the
presence of [H(Et2O)2][BAr4F] or [(C5H5)2Fe][BAr4F]+, the latter acting as a selective
reagent for the removal of the protecting group Cp* (= C5Me5). The reaction
mechanism involving alkyl-group transfer and disproportionation of intermediate
Zn(I) species as well as the electronic structure of these clusters will be discussed.
Figure 1. Series of first examples of ligand protected zinc clusters.
References:
[1] H.-G. Schnöckel, Dalton. Trans. 2008, 4344-4362.
[2] A. Aguado, A. Vega, A. Lebon, B. von Issendorff, Angew. Chem. Int. Ed., 2015, 54, 2111-2115.
[3] S. Zhen, K. Seff, J. Phys. Chem. B, 1999, 103, 6493-6497.
[4] (a) U. Häußermann, P. Viklund, C. Svensson, S. Eriksson, P. Berastegui, S. Lidin, Angew. Chem.
Int. Ed., 1999, 38, 488-492; (b) P. Viklund, C. Svensson, S. Hull, S. I. Simak, P. Berastegui, U.
Häußermann, Chem. Eur. J., 2001, 7, 5143-5152.
[5] K. Freitag, C. Gemel, P. Jerabek, M. I. Oppel, R. W. Seidel, G. Frenking, H. Banh, K. Dilchert, R.
A. Fischer, Angew. Chem. Int Ed., 2015, DOI: 10.1002/anie.201410737.
Poster presentation - P142
Zinc-Zinc Interactions in Zinc Containing Complexes and Clusters
Kerstin Freitag, Christian Gemel, Rüdiger Seidel, Paul Jerabek, Gernot Frenking and
Roland A. Fischer*
kerstin.freitag@rub.de
Inorganic Chemistry II, Ruhr-University Bochum
Universitätsstraße 150, GER-44801, Bochum
On the molecular scale, interactions of organozinc units with transition metals have
become important and many compounds and clusters have been reported in the recent
past.[1] In this context of our studies, the triangular compounds [Zn3Cp*3]+ and
[Zn2CuCp*] can be described as the most simple „building blocks“ for zinc and
mixed metal clusters. Theoretical calculations demonstrate a σ-aromatic nature and
thus strong analogies to the electronic structure of [H3]+.[2] Following there is an
analogy between H2and the .ZnCp* dimer [Zn2Cp*2], also shown by simple „addition
reactions“ of [Zn2Cp*2] to transition metal centers LnM, forming complexes of the
general type [LnM(ZnCp*)2], which mirrors „oxidative addition“ reactions of H2 to
electron rich unsaturated transition metal fragments. Against this background the
investigation of Zn2M complexes exhibiting Zn-Zn interactions, as analogues to nonclassical dihydrogen Kubas type complexes, aroused our interest.[3] Very recently
complexes, revealing shorter Zn-Zn distances as found for the (distorted) hexagonal
closest packed structure of metallic zinc (2.664(1) Å), have been isolated and
characterized, namely [Ni(ZnCp*)(ZnMe)(PMe3)3] (d(Zn-Zn) = 2.525(1) Å) and
[Pd(ZnCp*)4(CNtBu)2] (2.595(2) and 2.609(2) Å). Latest results on zinc-zinc
interactions in zinc containing complexes and clusters, based on theoretical
calculations as well as structural properties, are presented in this contribution.
Figure 1. Zn-Zn distances in [Zn2Cp*2], [Zn3Cp*3]+ and [Pd(ZnCp*)4(CNtBu)2].
References:
[1] K. Freitag, H. Banh, C. Gemel, R. W. Seidel, S. Kahlal, J.-Y. Saillard, R. A. Fischer, Chem. Comm.
2014, 50, 8681-8684.
[2] K. Freitag, C. Gemel, P. Jerabek, M. I. Oppel, R. W. Seidel, G. Frenking, H. Banh, K. Dilchert, R.
A. Fischer, Angew. Chem. Int. Ed. 2015, 10.1002/anie.201410737R1.
[3] G. J. Kubas, Proc. Natl. Acad. Sci. U. S. A. 2007, 104, 6901-6907.
Poster presentation - P143
Two Alternative Approaches to Access Mixed Hydride-Amido Zinc
Complexes: Synthetic, Structural and Solution Implications
Andrew J. Roberts, Stuart D. Robertson, Eva Hevia*
andrew.roberts@strath.ac.uk
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde
Glasgow, G1 1XL, UK
Molecular zinc hydrides have recently received much attention as non-precious metal
catalysts for homogenous hydrosilylation and hydroboration processes.[1] However,
despite this increasing interest, only a few well-defined examples are known.[1,2]
Highlighting the structural and stoichiometric diversity in zinc-hydride chemistry, this
poster explores the synthesis of NHC-stabilized mixed amido-hydride zinc complexes
using bis(amide) Zn(HMDS)2 (HMDS= 1,1,1,3,3,3-hexamethyldisilazide) as a
precursor and two alternative hydride sources, namely dimethylamine borane
(DMAB) and phenylsilane PhSiH3 (Figure). By combining X-ray crystallography with
advanced NMR spectroscopic studies (including DOSY NMR experiments), new
insights into the constitution of these new compounds will be discussed.[3]
References:
[1] (a) A. Rit, T.P. Spaniol, L. Maron, J. Okuda, Angew. Chem. Int. Ed., 2013, 52, 4664 (b) P.A.
Lummis, M.R. Momeni, M.W. Lui, R. McDonald, M.J. Ferguson, M. Miskolzie, A. Brown, E. Rivard,
Angew. Chem. Int. Ed., 2014, 53, 9351.
[2] (a) J. Spielmann, D. Piesik, B. Wittkamp, G. Jansen, S. Harder, Chem. Commun. 2009, 3455. (b) A.
Rit, T. P. Spaniol, L. Maron, J. Okuda, Organometallics, 2014, 33, 2039.
[3] A. J. Roberts,W. Clegg, A. R. Kennedy,M. R. Probert,S. D. Robertson, E. Hevia, Dalton Trans.
2015, advance article.
Poster presentation - P144
Investigations on selenidozincates and –cadmates in ionic liquids
Isabell Nußbruch, Stefanie Dehnen*
Nussbruch@students.uni-marburg.de
Department of Chemistry, Philipps University of Marburg
Hans-Meerwein-Str. 4, D-35032 Marburg
Recently the first top-down strategy for the deconstruction of a three-dimensional
framework in ionic liquids was reported.[1] The starting material was the 3Dselenidostannate-framework 3D-K2[Sn2Se5] (3D-1), which was thermally converted in
[BMIm][BF4] and the presence of an amine through a 2D layered phase (2D-1) to a
1D-chain structure (1D-1), back to a 3D-network (3D-2).[1] Furthermore, it is known
that selenidomercurates as well as selenidocadmates form 2D-layered phases and 3Dframework structures.[2][3] Preparations of phases of KxZnySez and KxCdySez with
different compositions followed by investigations on their behavior in and with ionic
liquids are studied. The solid phases are obtained as powders by heating K2Se and
ZnSe or CdSe in stoichiometric amounts in a quartz tube with an oxygen burner.
Ionothermal treatment of these solid phases is expected to lead to new interesting
structural changes and properties.
Figure 1. Illustration of the structural changes of 3D-K2[Sn2Se5] by ionothermal treatment.
References:
[1] Y. Lin, D. Xie, W. Massa, L. Mayrhofer, S. Lippert, B. Ewers, A. Chernikov, M. Koch, S. Dehnen,
Chem. - Eur. J. 2013, 19, 8806–8813.
[2] M. G. Kanatzidis, Y. Park, Chem. Mater. 1990, 2, 99–101.
[3] E. A. Axtell, J.-H. Liao, Z. Pikramenou, M. G. Kanatzidis, Chem. - Eur. J. 1996, 2, 656–666.
Poster presentation - P145
Bottom-Up! Intermetallic Nickel Gallium Molecular Clusters and
Complexes as Potential Precursors for Intermetallic Nanoparticles
Katharina Dilchert, Jana Weßing, Christian Gemel and Roland A. Fischer*
katharina.dilchert@rub.de
Chair of Inorganic Chemistry II – Organometallics & Materials
Ruhr-University Bochum, Universitätsstr. 150, GER-44801, Bochum
The low coordinate organo group 13 species ER (E = Al, Ga, In, R = Cp*, C(SiMe3)3,
Cp* = pentamethylcyclopentadienyl) of oxidation state +I are potent ligands at
transition metal centers and provide new perspectives for bottom-up intermetallic
cluster and nano material synthesis. In particular, ECp* ligands (E = Ga, Al, In) are
isolobal to CO, phosphines, NHC ligands and feature Cp* as fluxional and even
removable group. For the d10 metal triad Ni, Pd and Pt a number of small clusters
[Ma(ECp*)b] (a = 1, 2, 3)[1] is known. Such compounds show perspectives as
precursors for bimetallic Ni/Ga nanoparticles (suitable catalysts for alkyne
semihydrogenation) by hydrogenolysis or microwave induced decomposition in
organic solvents or ionic liquids (ILs).[2] Interestingly, examples for high nuclearity
clusters [MaLb] (a >> b, a >> 3) with L = PPh3 and/or CO are numerous. In contrast,
for L = ECp* the maximum nuclearity of the d10 metal core remained at a = 3, so far.
In this contribution we want to present the synthesis and characterization of
[Ni8(GaCp*)6], the first example of a homoleptic “intermetalloid” cluster
[Ma(ECp*)b] with a > b and a > 3. Single crystal XRD studies suggest a distorted
cubic structure of the Ni8core, which is face-capped by six GaCp* ligands. Liquid
injection field desorption mass spectrometry (LIFDI)-MS, however, reveals a
dominant signal for [Ni7(GaCp*)6]+ and only traces of [Ni8(GaCp*)6]. The details on
the synthesis, structural and spectroscopic characterization of [Nin(GaCp*)6] (n = 7, 8)
as well as the decomposition of the cluster to yield bimetallic Ni/Ga nanoparticles will
be presented and discussed.
Figure 1. Synthesis and structure of [Nin(GaCp*)6] (n =7,8) and LIFDI-MS data.
References:
[1] T. Steinke, C. Gemel, M. Winter, R. A. Fischer, Chemistry – A European Journal 2005, 11, 16361646.
[2] K. Schuette, A. Doddi, C. Kroll, H. Meyer, C. Wiktor, C. Gemel, G. van Tendeloo, R. A. Fischer,
C. Janiak, Nanoscale 2014, 6, 5532-5544.
Poster presentation - P146
Incorporation of Small Molecules in Fullerene-like Supramolecules
Claudia Heindl, Manfred Scheer*
Claudia.Heindl@ur.de
Institute of Inorganic Chemistry, University of Regensburg
Universitätsstraße 31, GER-93040 Regensburg
Supramolecular aggregates with defined inner cavities are in focus of current
research, especially because of their application as molecular container. A wide
variety of metal complexes with vacant coordination sites and linking units act as
building blocks for its preparation using the self-assembly concept. However, the
linkage is mostly restricted to ligands with nitrogen or oxygen as donating atoms.
It is shown, that also the use of pentaphosphaferrocene [Cp Fe(η5-P5)] (Cp* = C5Me5)
and CuX (X = Cl, Br, I) enables the formation of discrete supramolecules. Their
scaffold only consists of five- and six-membered rings and displays a non-carbon IhC80 fullerene analogue. In addition, they are capable to encapsulate small molecules,
such as o-carborane[1] or ferrocene.[2]
In order to examine the required properties of templates to be incorporated, different
molecules with distinctive features were tested. Herein, we are able to present that
also less symmetrical templates, like [(η7-C7H7)V(η5-C5H5)] and P4S3 can be trapped
within the cavity of these spheres.
Figure 1. Scaffold of a 80-vertex nanoball (left) and the whole sphere with encapsulated P4S3
(right).
References:
[1] M. Scheer, A. Schindler, C. Gröger, A. V. Virovets, E. V. Peresypkina, Angew. Chem. Int. Ed.
2009, 48, 5046.
[2] A. Schindler, C. Heindl, G. Balázs, C. Groeger, A. V. Virovets, E. V. Peresypkina, M. Scheer,
Chem. Eur. J. 2012, 18, 829.
Poster presentation - P147
Rational molecular design: common-sense chemistry
R. Andrew Davies,* Michael A. Beckett, Charlotte L. Jones, James S. Maskery,
Christopher D. Thomas
r.a.davies@bangor.ac.uk
School of Chemistry, Bangor University
Bangor, LL57 2UW, UK.
Conformational analysis of potential energy hypersurfaces is a laborious task even
with recent advances in computing power. Bond counting rules (BCRs)[1] compare
strengths of interatomic interactions allowing qualitative energetic predictions for
specific atomic arrangements. Quantitative BCRs were developed for
polyhydroxybenzoquinone dyes. Intramolecular H-bonding (with associated ring
formation in QTAIM analyses) stabilizes conformations by ca. 20 kJ·mol-1, whilst
H…H interactions must be avoided. The applicability the BCR approach to inorganic
ring systems will be demonstrated using the [B6O7(OH)6]2- polyborate anion which
contains a central trivalent “O+” atom at the junction of three rings (Figure 1).
Intramolecular H-bonding stabilizes conformer A by 20 kJ·mol-1 relative to conformer
B.
Figure 1. Hexaborate [B6O7(OH)6]2- structures: conformer A (middle), B (right).
Acknowledgements: We wish to thank the European Social Fund (ESF) for funding of a KESS
(Knowledge Economy Skills Scholarships) PhD studentship.
References:
[1] (a) M. Mattesini, S.F. Matar, Int. J. Inorg. Mater., 2001, 943-957; (b) M. Mattesini, S.F. Matar,
Comp. Mater. Sci., 2001, 107-119; (c) X.F. Fan, Z. Zhu, Z. X. Shen, J.L. Kuo, J. Phys. Chem. C, 2008,
15691-15696.
Poster presentation - P148
New ionic liquids containing the 2-Phosphaethynolate-anion
Maximilian Jost, Lars H. Finger, Carsten von Hänisch, Jörg Sundermeyer*
jostm@students.uni-marburg.de
Fachbereich Chemie, Philipps-Universität Marburg
Hans-Meerwein-Straße 4, GER-35032, Marburg
In 1992 the heavier congener of the cyanate ion the PCO--anion was first synthesized
by Becker et al.[1] In recent years the chemistry of this anion has been explored, in
particular by the groups of Grützmacher and Goicoechea.[2–4] The counterions of this
anion are usually alkaline or alkaline earth metals, organic counterions are still
unknown. Herein we present the first ionic liquids (IL) with the PCO--anion
containing different organic counterions, which were prepared starting from the
methylcarbonateanion, circumventing the application of highly reactive LiP(SiMe3)2.
Furthermore we investigated the reactivity of those IL’s against
Tris(trimethylsilyl)stibane. In the course of the reaction we could not obtain the
heavier congener SbCO--anion, instead we crystallized [P(nBu)3Me]3Sb11, the first
Ufosan-structure which contains a [Sb11]3- anion with organic cations.
Figure 1. Above: Schematic pathway to novel compounds containing the PCO--anion and
molecular structure of C(NMe2)3PCO. Below: Molecular structure of [P(nBu)3Me]3Sb11.
References:
[1] G. Becker, W. Schwarz, N. Seidler, M. Westerhausen, Z. anorg. allg. Chem. 1992, 612, 72–82.
[2] F. F. Puschmann, D. Stein, D. Heift, C. Hendriksen, Z. A. Gal, H. F. Grützmacher, H. Grützmacher,
Angew. Chemie - Int. Ed. 2011, 50, 8420–8423.
[3] A. R. Jupp, J. M. Goicoechea, J. Am. Chem. Soc. 2013, 135, 19131–19134.
[4] A. R. Jupp, J. M. Goicoechea, Angew. Chemie - Int. Ed. 2013, 52, 10064–10067.
Poster presentation - P149
Generation of a tripodal Schiff-base metalloligand
Francisco M. García-Valle, Tomás Cuenca, Vanessa Tabernero, Jesús Cano* and
Marta E. G. Mosquera*
francisco.garciav@edu.uah.es
Departamento de Química Orgánica y Química Inorgánica, University of Alcalá
Facultad de Farmacia, Ctra. Madrid-Barcelona (Autovía A2) Km. 33,600,Campus
Universitario, 28871-Alcala de Henares, Madrid. Spain.
Schiff-base compounds are very attractive ligand precursors due to their steric and
electronic properties and their amenability to modification. Their straightforward
preparation and easy purification make them very popular candidates for the
preparation of a wide variety of metallic compounds.[1] However, not many
heterometallic derivatives containing main group metals have been described with
Schiff-base ligands, even though homometallic derivatives show very interesting
reactivities. In particular, aluminium or alkali Schiff-base compounds are very active
in catalytic polymerization processes,[2] and also in other activation reactions such as
nucleophilic additions to carbonyl compounds.[3] In our group, we are interested in
generating a new class of Schiff-base heterometallic complexes using main group
metals. These studies have allowed us to isolate new compounds and the formation of
a novel aluminate tripodal metalloligand (Figure 1). The behaviour of these species in
polymerization processes and activation of small molecules is being analysed.
Figure 1. Tripodal aluminate metalloligand.
References:
[1] (a) Makio, H.; Terao, H.; Iwashita, A.; Fujita, T. Chem. Rev. 2011, 111, 2363 ; (b) García-Valle, F.
M.; Estivill, R.; Gallegos, C.; Cuenca, T.; Mosquera, M. E. G.; Tabernero, V.; Cano, J.
Organometallics 2015, 34, 477.
[2] (a) Zhang, J.; Jian, C.; Gao, Y.; Wang, L.; Tang, N.; Wu, J. Inorg. Chem. 2012, 51, 13380 ; (b)
Zhang, J.; Xiong, J.; Sun, Y.; Tang, N.; Wu, J. Macromolecules 2014, 47, 7789. (c) Nomura, N.; Ishii,
R.; Yamamoto, Y.; Kondo, T. Chem.-Eur. J. 2007, 13, 4433.
[3] Ternel, J.; Agbossou-Niedercorn, F.; Gauvin, R. M. Dalton Trans. 2014, 43, 4530.
Poster presentation - P150
PREPARATION OF CONDUCTING PANI GRAFT POLYMERS
Nazmiye Kilic,(a) E. Busra Celebia,b, Adem Kilic, Serkan Yesilot, Ferda
Hacivelioglu(a)*
ferda@gtu.edu.tr
Gebze Technical University
PK.141, 41400, Gebze, KOCAELI
Since the discovery of doped polyacetylene (PA) as a conducting polymer in 1977[1] it
has been found that only a few polymers, polythiophene (PTh), polypyrrole (PPy) and
polyaniline (PANI) are stable enough under environmental conditions to be
incorporated in practical applications. In these important conducting polymers, PANI
has many advantages over other conducting polymers. PANI is thermally stable and
can be easily synthesized chemically and electrochemically via oxidative
polymerization in various organic solvents and/or in aqueous media[2]. However,
similar to other pi-conjugated polymers, the application range of PANI, is limited due
to its insolubility and infusibility. Therefore, in order to improve the solubility and
induce fusibility of the stiff chain of PANI, various procedures have been proposed.
Polyphosphazenes are inorganic polymers comprised of a backbone of alternating P
and N atoms with two side groups linked to each phosphorus atom. Although the
structure of these polymers are written as a sequence of alternating single and double
bonds, in fact the bonding is not of the classical pπ-pπ type as in their counterparts in
classical organic conjugated polymers. The most attractive properties of the
polyphosphazenes are the stability of the inorganic chain to oxidation, reduction, and
photochemical, or thermal bond cleavage, provided appropriate selection of side
groups are attached to phosphorus atom [3]. In this study we investigated preparation
of PANI grafted poly[bis(3-methylphenoxy(sulfonicacid)]phosphazene (PSAP) via
chemical oxidation. The resulting polymers have been characterized by FT-IR, 1H and
31
P NMR and thermal, surface, optical and conductivity properties of the resulting
graft polymers have been investigated.
Acknowledgements: This research was supported by The Scientific and Technological Research
Council of Turkey [TUBITAK, Project no: 114Z314]. We also thank to COST action Smart Inorganic
Polymers (SIPs, www.sips-cost.org ).
References:
[1] Shirakawa H, Louis EJ, MacDiarmid AG, Chiang CK, Heeger AJ., Chem Commun., 1977, 578–80.
[2] Syed AA, Dinesan MK. Talanta, 1991; 38, 815–37.
[3] Allcock H R. Chemistry and applications of polyphosphazenes, Wiley-Interscience, NY, 2003.
Poster presentation - P151
Methanol Synthesis in Silico. Quantumchemical Calculations on a
Cu4Zn3O3 Picomodel
Daniel Himmel, Marc Jäger, Ingo Krossing*
Daniel.himmel@ac.uni-freiburg.de
Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität
Freiburg
Albertstr. 1, D-79106 Freiburg im Breisgau
Methanol can be synthesized from hydrogen and carbon dioxide (or carbon
monoxide) on a copper-zinc oxide catalyst at temperatures above 200-250 °C and
pressures of 30-100 bar. Despite many speculations about possible intermediates, the
mechanism is poorly understood. We constructed a Cu4Zn3O3 cluster as smallestpossible approximation for the catalyst bulk phase which is small enough for highly
accurate ab inito calculations. Using high level quantumchemical methods, possible
intermediate species were screened and pathways constructed from them.
Figure 1. One possible catalytic circle. Gibbs energies were calculated with [DLPNOCCSD(T)/A(wC)VDZ – MP2/A(wC)VDZ + MP2/A(wC)VQZ] //B3LYP-D3(BJ)/def2TZVPP
Poster presentation - P152
Low valent Pentaaryl Cyclopentadienyl Fe, Co and Ni Complexes
Uttam Chakraborty,(a) Niels van Velzen,(b) Sjoerd Harder,(b) and Robert Wolf*(a)
uttam.chakraborty@ur.de
(a). Institute of Inorganic Chemistry, University of Regensburg, D-93040 Regensburg
(b) Chair of Inorganic and Organometallic Chemistry, University of ErlangenNürnberg, D-91058 Erlangen
Pentaaryl cyclopentadienyl ligands are attractive ligands for low-valent 3d metal ions,
because they can confer substantial kinetic stabilization due to their steric bulk and
promise to be less strongly electron donating than related alkyl-substituted
derivatives.[1,2] However, their use can be hampered by the ready formation of the
pentaaryl cyclopentadienyl radical.[2a,3,4] Here, we describe the synthesis and
reactivity of complexes of general formula [CpBMBr]2 (M = Fe, Co, Ni, CpB =
C5(C6H4-4-Et)5). Treatment of CpBK with [FeBr2(THF)2], CoBr2 and [NiBr2(DME)]
affords [CpBFeBr]2 (1), [CpBCoBr]2 (2) and [CpBNiBr]2 (3), respectively. Dimeric 1-3
display halide-bridged solid-state molecular structures and feature a high-spin
configuration for the metal atoms. The reaction of [CpBNiBr]2 (3) with
Ga(NacnacDipp) followed by the addition of KC8 leads to the Ni(I) complex 4, while
the direct reaction of 3 with KC8 generates a “Cp(b)Ni(I)” source which can be
trapped with several substrates, e.g. N-heterocyclic carbenes, S8 or TEMPO, leading
to the complexes 5-7 (Scheme 1).
Scheme 1. Synthesis of complexes 1–7.
References:
[1] a) W. Kläui, L. Ramacher, Angew. Chem. Int. Ed. Engl. 1986, 25, 97-98; b) H. Schumann, A.
Lentz, R. Weimann, J. Pickardt, Angew. Chem. Int. Ed. Engl. 1994, 33, 1731-1733; c) C. Ruspic, J. R.
Moss, M. Schürmann, S. Harder, Angew. Chem. Int. Ed. 2008, 47, 2121-2126.; d) L. D. Field, C. M.
Lindall, A. F. Masters, G. K. B. Clentsmith, Coord. Chem. Rev. 2011, 255,1733-1790.
[2] examples: a) H. Sitzmann, T. Dezember, W. Kaim, F. Baumann, D. Stalke, J. Kärcher, E. Dormann,
H. Winter, C. Wachter, M. Kelemen, Angew. Chem. Int. Ed. 1996, 35, 2872-2875; b) M. D. Walter, J.
Grunenberg, P. S. White, Chem. Sci. 2011, 2, 2120-2130; c) M. D. Walter, P. S. White, Inorg. Chem.
2012, 51, 11860-11872; d) H. Sitzmann, F. H. Köhler, et al. Organometallics 2013, 32, 6298-6305
[3] J.- . Thépot, C. apinte, J. Organomet. Chem. 2002, 656, 146-155.
[4] S. Heinl, S. Reisinger, C. Schwarzmaier, M. Bodensteiner, M. Scheer, Angew. Chem. Int. Ed. 2014,
53, 7639-7642.
Poster presentation - P153
Reactions and characteristics of a cationic Ni(I)-Complex
Miriam Schwab, Daniel Himmel, Melanie Wernet, Philippe Weis, Andreas Peter,
Ingo Krossing*
ingo.krossing@ac.uni-freiburg.de
Institut für Anorganische und Analytische Chemie, Freiburger
Materialforschungszentrum (FMF)
Stefan-Meier-Str. 21, GER-79104, Freiburg
Weakly coordinating anions (WCAs) are often used to stabilize high reactive cations.
The single negative charge of WCAs, which is delocalized over a large surface, leads
to only little interactions between the anion and the associated cation.[1] One of these
anions is the perfluoro-tert-butoxy aluminate which provides a cationic [NiI(cod)2]+
species (cod = 1,5-cyclooctadiene) as [Al(ORF)4]– (RF= C(CF3)3) salt. With a d9electron configuration Ni(I) is a very unstable species which usually needs strong σdonating ligands with for example phosphor and nitrogen donor atoms.[2]
[NiI(cod)2][Al(ORF)4] (1) as a powder indicates no oxygen or air sensitivity, whereas
a solution in CH2Cl2 shows a changed signal in EPR spectrum when oxygen is
present. Reaction tests with mono- or bidentate phosphine ligands resulted in ligand
exchanges (Figure 1), whereas utilization of more coordinating solvents like THF lead
to disproportionation to Ni0 and [Ni(THF)6][Al(ORF)4]2.
Figure 1. Ligand exchange of 1 with PPh3 and dppp (1,3-bis(diphenylphosphino)propane).
Acknowledgements: This work was supported by the Freiburger Materialforschungszentrum of the
University of Freiburg (FMF) and funded by the ERC project UniChem
References:
[1] I. Krossing, I. Raabe, Angew. Chem. 2004, 116, 2116–2142.
[2] a) M. Vogt, B. de Bruin, H. Berke, M. Trincado, H. Grützmacher, Chem. Sci. 2011, 2, 723–727; b)
D. C. Bradley, M. B. Hursthouse, R. J. Smallwood, A. J. Welch, J. Chem. Soc., Chem. Commun. 1972,
872–873; c) A. Gleizes, M. Dartiguenave, Y. Dartiguenave, J. Galy, H. F. Klein, J. Am. Chem. Soc.
1977, 99, 5187–5189; d) L. Sacconi, P. Dapporto, P. Stoppioni, J. Am. Chem. Soc. 1975, 97, 5595–
5596.
Poster presentation - P154
The reactivity of [(C10H15)Fe(5-P5)] and [(C5H2tBu3)Ni(3-P3)]
Eric Mädl, Manfred Scheer*
Eric.Maedl@ur.de
Institute of Inorganic Chemistry, University of Regensburg
Universitätsstr. 31, GER-93053, Regensburg
The long known pentaphosphaferrocene [Cp*Fe(5-P5)] shows a divers reactivity
pattern. Whereas in the past the reactions with various organometallic reagents have
been broadly investigated,[1] its use as a building block in coordination and
supramolecular chemistry was recently discovered by our group.[2] Moreover, first
reactivity with nucleophiles[3] and reducing agents[4] was recently reported by us. We
report here on the reactivity of pentaphosphaferrocene [Cp*Fe(5-P5)] towards
LiNMe2, yielding a rare P5-envelope structural motif and the subsequent reactions
with transition metal halides of the type [Cp'''MX]2 (M = Fe, Co; X = Cl, Br).
Furthermore, the reactivity of [Cp'''Ni(3-P3)] towards NaNH2, forming an anionic
triple-decker, is described, which can be subsequently oxidized.
Scheme 1. The different reactivity patterns of pentaphosphaferrocene and [Cp'''Ni(3-P3)].
References:
[1] O. J. Scherer, Acc. Chem. Res. 1999, 32, 751–762.
[2] M. Scheer, Dalton Trans. 2008, 4372-4386.
[3] M. V. Butovskii, G. Balázs, M. Bodensteiner, E. V. Peresypkina, A. V. Virovets, M. Scheer,
Angew. Chem. 2013, 125, 3045-3049.
[4] E. Mädl, M. V. Butovskii, G. Balázs, E. V. Peresypkina, A. V. Virovets, M. Seidl, M. Scheer,
Angew. Chem. Int. Ed. 2014, 53, 7643-7646.
Poster presentation - P155
Dinuclear Iron and Ruthenium Complexes Containing Naphthalene
as a Bridging Ligand
Dirk Herrmann, Jennifer Malberg and Robert Wolf*
dirk.herrmann@ur.de
University of Regensburg, Institute of Inorganic Chemistry
Universitätsstr. 31, 93053 Regensburg Germany
Bimetallic complexes with polyaromatic hydrocarbon ligands may display a variable
degree of electronic coupling between the metal centers, depending on the nature of
the bridging ligand.[1] Various polyarene ligands have been used in the past, but
binuclear complexes containing the simplest polyarene naphthalene are scarce.[2]
Here, we describe an investigation of the properties of naphthalene as a bridging
ligand in dinuclear iron and ruthenium complexes, including heterobimetallic
derivatives. We report the synthesis and characterization of a series of compounds of
type [CpRM(µ‑naphthalene)M'Cp*] (CpRM = Cp*Fe, Cp'Fe, and Cp*Ru; Cp*M' =
Cp*Fe, and Cp*Ru; Cp* = C5Me5, Cp' = C5H2tBu3).[3] The molecular structures
feature an anti-facial arrangement where the metal cations are bound to opposite sides
of the naphthalene molecule. An investigation of the redox properties (cyclic
voltammetry and UV-vis spectroelectrochemistry) in conjunction with DFT
calculations reveals the strong electronic coupling between the metal atoms in these
complexes. Monocations [CpRM(µ-naphthalene)MCp*]+ were isolated by oxidation
of the neutral species and characterized by X-ray crystallography and spectroscopic
techniques. These cations can be classified as borderline class II / class III compounds
in case of the FeFe and FeRu species, while the RuRu cation [Cp*Ru(µC10H8)RuCp*]+ appears to be a class III compound with full charge delocalization.[4]
References:
[1] reviews: a) A. Ceccon et. al., Coord. Chem. Rev. 2004, 248, 683-724; b) D. Astruc, Acc. Chem. Res.
1997, 30, 383-391; c) D. S. Perekalin, A. R. Kudinov, Coord. Chem. Rev. 2014, 276, 153-173.
[2] a) W. H. Morrison, E. Y. Ho, D. N. Hendrickson, J. Am. Chem. Soc. 1974, 96, 3603-3608; b) K.
Jonas, Pure Appl. Chem. 1990, 62, 1169-1174; c) U. Kölle, M. H. Wang, Organometallics 1990, 9,
195-198; d) H. Salembier, R. M. Chin et. al., Organometallics 2012, 31, 4838-4848.
[3] a) E.-M. Schnöckelborg, F. Hartl, T. Langer, R. Pöttgen, R. Wolf, Eur. J. Inorg. Chem. 2012, 16321638; b) J. Malberg, R. Wolf et. al., Organometallics 2013, 32, 6040-6052.
[4] M. B. Robin, P. Day, Adv. Inorg. Chem. Radiochem. 1967, 10, 247-422.
[5] D. Herrmann, E. Lupton, F. Hartl, R. Wolf, manuscript in preparation.
Poster presentation - P156
Transformations of Small Inorganic Molecules by Low-valent
Transition Metalate Anions and Transition Metal Radicals
Robert Wolf,* Uttam Chakraborty,(a) Stefan Pelties,(a) Niels van Velzen,(b) and
Sjoerd Harder(b)
robert.wolf@ur.de
(a) University of Regensburg, Institute of Inorganic Chemistry, D-93040 Regensburg;
(b) Chair of Inorganic and Organometallic Chemistry, University ErlangenNürnberg, Egerlandstraße 1, D-91058 Erlangen
This talk will discuss the chemistry of new low-oxidation state cyclopentadienyl iron,
cobalt and nickel complexes. The first part will describe the synthesis of Nheterocyclic carbene-stabilized cyclopentadienylnickel(I) radicals.[1] The complexes
have a modular structure that allows the modification of their steric and electronic
properties. The reactivity of these new nickel(I) radicals with radical traps such as
white phosphorus and elemental sulfur will be examined. The second part will discuss
the chemistry of new pentarylcyclopentadienyl complexes.[2] These uncommon Cp
derivatives are able to stabilize compounds with unusual structures and reactivity
patterns as illustrated for example by the synthesis of the first
tetraphosphacyclobutadiene iron complex, [CpAr5Fe(cyclo-P4)]- and the dinuclear
hexasulfide [(CpAr5Ni)2(µ-S6)] (Figure 1).
Figure 1. Reactivity of new cyclopentadienyl iron and nickel complexes.
Acknowledgements: We thank Moritz Modl and Prof. Manfred Scheer (University of Regensburg) for
collaborating on CpBig chemistry.
References:
[1] S. Pelties, D. Herrmann, B. de Bruin, F. Hartl, R. Wolf, Chem. Commun. 2014, 50, 7014-7016.
[2] a) W. Kläui, L. Ramacher, Angew. Chem. Int. Ed. Engl. 1986, 25, 97-98; b) H. Schumann, A.
Lentz, R. Weimann, J. Pickardt, Angew. Chem. Int. Ed. Engl. 1994, 33, 1731-1733; c) C. Ruspic, J. R.
Moss, M. Schürmann, S. Harder, Angew. Chem. Int. Ed. 2008, 47, 2121-2126.; d) L. D. Field, C. M.
Lindall, A. F. Masters, G. K. B. Clentsmith, Coord. Chem. Rev. 2011, 255,1733-1790.
Poster presentation - P157
Coordination chemistry of new di-/monoanionic ferrocene-based di/phosphido chelate ligands
Sandra Hitzel, Clemens Bruhn, Ulrich Siemeling
sandrahitzel@uni-kassel.de
Institute of Chemistry, University of Kassel
Heinrich-Plett-Str. 40, GER-34132, Kassel
The 1,1´-difunctionalisation of ferrocene with donor atoms like nitrogen and
phosphorus is of great interest in organometallic and coordination chemistry, in
particular in terms of catalytic applications.1 The resulting ligands can be categorized
as either neutral (L,L type, for example the well-known dppf ligand) or dianionic
(X,X type). During our investigations, we were able to isolate monoanionic (L,X
type) intermediates. Whereas N,N’-difunctionalised ferrocene frameworks of the type
[Fe{C5H4(NHR)}2] (1H2) and their diamido chelate ligand form [Fe{C5H4(NR)}2]2(1) are well established, the phosphorus homologues of 1H2are completely
underdeveloped. This fact is surprising in view of the great current interest in
transition metal phosphido complexes.2 The only representative known to date is
[Fe{C5H4(PHPh)}2] (2H2a).3 We will present a range of new [Fe{C5H4(PHR)}2]
derivatives (2H2b-e) bearing substituents of different steric and electronic
characteristics. Furthermore, results concerning their deprotonation and their
coordination behaviour e.g. towards nickel will be shown.
Figure 1. Diaminoferrocenes of type 1H2 and their deprotonated form 1.
Diphosphinoferrocenes of type 2H2 and their chelating coordination modes towards nickel.
References:
[1] Reviews: (a) Ferrocenes, eds. Togni, A., Hayashi, T. VCH, Weinheim, 1995 (b) Siemeling, U.,
Auch, T.-C. Chem. Soc. Rev. 2005, 34, 584
[2] Rosenberg, L. Coord. Chem. Rev. 2012, 256, 606
[3] Lane, E. M., Chapp, T. W., Hughes, R. P., Glueck, D. S., Feland, B. C., Bernard, G. M.,
Wasylishen, R. E., Rheingold, A. L. Inorg. Chem. 2010, 49, 3950
Poster presentation - P158
Applications of the five-membered ring products of cyclometalation
reactions as OLEDs
Iwao Omae
um5i-oome@asahi-net.or.jp
Omae Research Laboratories
335-23, Mizuno, Sayama, Saitama, 350 -1317, Japan
Cyclometalation reactions producing five-membered ring products progress
regioselectively and extremely easily by using many kinds of metal compounds with
various kinds of substrates because the produced five-membered ring compounds are
the most stable as compared with the other ring compounds such as four- and sixmembered rings [1-3]. Those massive five-membered ring products are applied in many
fields such as catalysts, OLEDs, pharmaceuticals, dye-sensitized solar calls, carbon
dioxide utilization, sensors, and so on. The summary of these applications are already
reported as a monograph in 2014 [3]. This research describes mainly on recent
developments in OLEDs. The OLED Handbook in 2014 reported that the largest uses
of OLEDs are not in TVs but mobile phones, digital cameras, wearable devices,
notebook PCs and tablets. The total annual sales of OLED displays exceeded $10
billion in 2013 [4]. The presence of a high field strength ligand such as N-heterocyclic
carbene (NHC) iridium compounds, in the compounds giving rise high energy
emissions, and consequently leading desired blue color emission needed for the
OLED applications. Neutral two-electron donors show pronounced s-donor ability
with little to no p-back bonding. Due to their strong s-electron-donating properties,
NHC ligands usually form strong bonds with most metal centers and are therefore
highly resistant towards decomposition. Thus, Luminescence Technology Corp.
(OLED maker) also manufactured mostly these carbene compounds as the OLED
products. Hence, these NHC iridium compounds such as imidazole-type carbene
compounds, are mostly expected to be the cyclometalated iridium compounds of great
promise as blue color emitting compounds for the OLED devices. The other
compounds used as the OLED devices are NCN tridentate compounds, 2phenylpyridine compounds, 2-phenylpyridine fluorinated compounds, phenyltriazole
compounds, 2,3'-bipyridine compounds and triphenyltriazole dendrimers.
References:
1. I. Omae, Chem. Rev. , 1979, 79, 287.
2. I. Omae, Organometallic Intramolecular- coordination Compounds, Elsevier, Amsterdam, 1986.
3. I. Omae, Cyclometalation Reactions: Five-Membered Ring Products as Universal Reagents,
Springer, Tokyo, 2014.
4. R. Mertens, A Guide to OLED Technology, Industry & Market, 2014 Ed.
Poster presentation - P159
Carbolithiation vs. Deprotonation: Control of the Reaction Behavior
of Allylamines towards Alkyllithium Reagents
Ulrike Kroesen, Lena Knauer, Carsten Strohmann*
ulrike.kroesen@tu-dortmund.de
Faculty of Chemistry and Chemical Biology, TU Dortmund University
Otto-Hahn-Str. 6, GER-44227, Dortmund
Lithiation reactions represent a manifold and important type of reaction in organic and
metalorganic synthesis. They allow the creation of highly reactive molecular building
blocks and further reactions with electrophiles. One challenge is the synthesis via
competing deprotonation and carbolithiation and the understanding of metastable
metalated species. In the presented results the main focus lies on allylamines and their
metalation using alkyllithium reagents as well as the Schlosser’s Base, directed by the
formation of inorganic ring intermediates.[1] Allylamines show high potential in the
use as homoenolate equivalents and enable the synthesis of otherwise inaccessible
building blocks, which are particulary significant in the synthesis of pharmaceuticals
and natural products.[2] The focus of this research lies on the influence of the
metalating reagent – particularly the alkali metal (Li, Na, K) – and on the structure
and stability of the synthesized compounds as well as the study of the regio- and
stereochemistry of the reactions depending on the alkyllithium reagent and the
solvent.
Figure 1. Carbolithiation vs. Deprotonation.
Acknowledgements: We are grateful to the Deutsche Forschungsgemeinschaft (DFG) and the Fonds
der Chemischen Industrie (FCI) for financial support.
References:
[1] (a) M. Schlosser, Pure Appl. Chem. 1988, 60, 1 27 b) . ochmann, J. Pospíšil, D.
Tetrahedron Lett. 1966, 2, 257.
[2] H. Ahlbrecht, G. Boche, K. Harms, M. Marsch, H. Sommer, Chem. Ber. 1990, 123, 1853.
ím,
Poster presentation - P160
Polyarene Metalates as Precatalysts for Hydrogenations: Scope and
Mechanism
Philipp Büschelberger,(a) Dominik Gärtner,(b) Babak Razaei Rad,(a) Axel Jacobi von
Wangelin (b)* and Robert Wolf (a)*
philipp.bueschelberger@ur.de
University of Regensburg, (a) Institute of Inorganic Chemistry, and (b) Institute of
Organic Chemistry
Universitätsstraße 31, D-93040 Regensburg
Catalytic hydrogenations constitute one of the most important operations for the
conversion of raw chemicals and the synthesis of fine chemicals and
pharmaceuticals.[1] In addition to the well-developed noble metal catalysts, there is
great interest in developing new catalysts based on more abundant first-row transition
metals.[2] We recently found that the bis(anthracene)cobaltate 1 is an active
precatalyst for the hydrogenation of alkenes, ketones and imines under mild
conditions.[3] Surprisingly, the iron analogue 2 is significantly less active. The poster
will compare the catalytic properties of 1 and 2 with a series of related alkene and
arene complexes 3–7, which feature iron and cobalt in different oxidation states.
Several of these complexes were found to be catalytically active, albeit none parallels
the properties of 1. Moreover, we will address the nature of the catalytically active
species. The results of NMR-monitoring studies and selective catalyst poisoning
experiments will be presented.
References:
[1] a) B. Plietker, Iron Catalysis in Organic Chemistry: Reactions and Applications, John Wiley &
Sons, 2008; b) B. Plietker, M. Beller, Iron Catalysis: Fundamentals and Applications, Springer, 2011.
[2] M. S. Holzwarth, B. Plietker, ChemCatChem 2013, 5, 1650–1679.
[3] a) W. W. Brennessel, V. G. Young, Jr., J. E. Ellis, Angew. Chem. Int. Ed. 2002, 41, 1211–1215; b)
D. Gärtner, A. Welther, B. Razaei Rad, R. Wolf, A. Jacobi von Wangelin, Angew. Chem. Int. Ed.
2014, 53, 3722–3726; c) W. W. Brennessel, R. E. Jilek, J. E. Ellis, Angew. Chem. Int. Ed. 2007, 46,
6132–6136.
Poster presentation - P161
Studies on heteroleptic Cp*Be-R compounds
Dominik Naglav, Briac Tobey, Stephan Schulz*
dominik.naglav@uni-due.de
Faculty of Chemistry, University of Duisburg-Essen
Universitatsstr. 5-7, GER-45141, Essen
The authors present extensive studies on several hitherto unknown heteroleptic
Cp*BeX compounds (Cp* = pentamethylcyclopentadienyl / X = F [1], Cl [2], Br [3], I
[4]) focussing on solid state structures, theoretical investigations and 9Be-NMR. We
present the solid state structures of 2, 3 and 4 and their solvent depending 9Be-NMR
shifts. They crystallize isostructurally as colorless crystals in the monoclinic space
group P21/c with two independent molecules in the unit cell. To get more details
about the bonding situations in these complexes we performed ELF (electron
localization function) and LOL (localized orbital localization), as well as NBO
(natural bond orbital) analysis on the geometry optimized structures from DFT
calculations (def2-TZVPP/B3LYP) including Cp*BeF. The ELF figures and NBO
charges show a highly polarized Be-center in the complexes, whereas the LOL
analyses demonstrate an increasing covalent character of the Be-X bond with higher
atomic numbers of the halide. The charge on the Be center decreases with the increase
of the covalency of the beryllium halide bond.
Figure 1. 2D ELF plots of [1] to [4] of in the C(ring)-Be-X-plane and 3D LOL plots of 1 to 4
with v = 0.53.
References:
[1] D. Naglav, A. Neumann, B. Tobey, D. Bläser, C. Wölper, S. Schulz, Organomet., manuscript in
preparation.
Poster presentation - P162
Calcium Hydride Catalyzed Highly 1,2-Selective Pyridine
Hydrosilylation
Heiko Bauer,(a) Julia Intemann,(b) Jürgen Pahl,(a) Sjoerd Hardera,*
Sjoerd.harder@fau.de
a: Department of Inorganic and Organometallic Chemistry, Friedrich-Alexander
University Erlangen-Nürnberg, Egerlandstraße 1, 91058 Erlangen, Germany
b: Stratingh Institute for Chemistry, Nijenborgh 4, 9747AG Groningen, The
Netherlands
Early work by Ashby et al. showed that addition of MgH2to pyridine gives a mixture
of 1,2- and 1,4-dihydropyridides (DHP), but subsequent heating led to exclusive
isomerization to the 1,4-derivative.[1-2] Similarly, dearomatization of pyridine by bdiketiminate magnesium hydride intermediate, yields pure 1,4-DHP after heating.[3],[4]
We recently found that a coupled β-ketiminate magnesium hydride complex reacts
with pyridine to give exclusively the 1,2-DHP product, with less than 10% conversion
to 1,4-DHP after excessive heating.[5] Unfortunately, under a catalytic regime only
mixtures of 1,2- and 1,4-products could be found. Reaction of the calcium hydride
complex (DIPPnacnac-CaH·THF)2 with pyridine is much faster and more selective
than that of the corresponding magnesium hydride complexes. With a range of
pyridine, picoline and quinoline substrates, exclusive transfer of the hydride ligand to
the 2-position is observed and also at higher temperatures no 1,2→1, isomerization
is found. The product DIPPnacnac-Ca(1,2-dihydropyridide)·(pyridine) is not stable
towards ligand exchange into homoleptic calcium complexes and could not be
isolated, but the crystal structure of the homoleptic product from calcium hydride
reduction of isoquinoline, Ca(1,2-dihydroisoquinolide)2·(isoquinoline)4, has been
determined. This unusual 1,2-selectivity in the dearomatization of pyridines was
utilized in catalysis. Whereas hydroboration of pyridine with pinacol borane with a
calcium hydride catalyst gave only minor conversion, the hydrosilylation of pyridine
and quinolines with PhSiH3yields exclusively 1,2-dihydropyridine and 1,2dihydroquinoline silanes with 80-90% conversion. These calcium complexes
represent the first catalysts for the 1,2-selective hydrosilylation of pyridines.
References:
[1] E. C. Ashby, A. B. Goel, J. Am. Chem. Soc. 1977, 99, 310
[2] E. C. Ashby, A. B. Goel, J. Chem. Soc. Chem. Commun. 1977, 169.
[3] M. S. Hill, D. J. MacDougall, M. F. Mahon, Dalton Trans. 2010, 39, 11129.
[4] M. S. Hill, G. Kociok-Köhn, D. J. MacDougall, M. F. Mahon, C. Weetman, Dalton Trans. 2011,
40, 12500.
[5] J. Intemann, M. Lutz, S. Harder, Organometallics 2014, 33, 5722.
Poster presentation - P163
Synthesis and reactivity of an unprecedented cationic Mg βdiketiminate complex
Jürgen Pahl, Tom Stennett, Harmen Zijlstra, Sjoerd Harder*
juergen.pahl@fau.de
Department of Chemistry and Pharmacy, Friedrich-Alexander Universität ErlangenNürnberg, Egerlandstraße 1, 91058, Erlangen, Germany
Cationic complexes of group 3 and 4 metals are well known; they represent models of
active species or potential intermediates in, for instance, the polymerization of αolefins.[1] By contrast, occurrences of alkaline earth metal cationic complexes remain
rather scarce[2], especially ones employing β-diketiminate ligand systems.[3] Besides
the β-diketiminate ligand, these complexes rely on strongly coordinating solvents
such as pyridine and tetrahydrofuran for stabilization. Abstraction of a butyl group
from DIPPNacnacMgBu in aromatic solvents affords a cationic Mg complex
containing a coordinated arene molecule (1, Figure 1). Up until now the coordination
of unpolar solvents like benzene and toluene to alkaline earth metals could only be
observed for select barium compounds.[3]
Figure 1. Synthesis of a cationic β-diketiminate magnesium complex.
References:
[1] M. Bochmann, Organometallics 2010, 29, 4711-4740.
[2] a) M. G. Cushion, P. Mountford, Chem. Commun., 2011, 47, 2276–2278; b) B. J. Ireland, C. A.
Wheaton, P. G. Hayes, Organometallics, 2010, 29, 1079-1084; c) C. Lichtenberg, P. Jochmann, T. P.
Spaniol, J. Okuda, Angew. Chem. Int. Ed. 2011, 50, 5753 –5756.
[3] B. Liu, V. Dorcet, L. Maron, J. Carpentier, Y. Sarazin, Eur. J. Inorg. Chem. 2012, 3023–3031
[4] L. Bonomo, E. Solari, R. Scopelliti, C. Floriani, Chem. Eur. J., 2001, 7, 1322-1332.
Poster presentation - P164
Regioselective deprotonation of N-heterocyclic molecules using ßdiketiminate stabilized magnesium bases
Laia Davin, Alberto Hernán-Gómez, Eva Hevia*
laia.davin-cardona@strath.ac.uk
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde
295 Cathedral Street, G1 1XL, Glasgow, UK
Despite their prevalence in many pharmaceuticals and natural products, the
regioselective metallation of N-heterocyclic molecules such as diazines or pyridines
using polar organometallic reagents still remains an important challenge in
synthesis.[1] This is primarily due to the low stability of the generated metallated
intermediates which undergo fast decomposition at room temperature.[2] In this poster,
we present our findings in developing novel magnesium reagents supported by βdiketiminate ligands as a new synthetic strategy for the regioselective deprotonation
of sensitive N-heterocyclic molecules. Using kinetically activated amide base 1,[3] it is
possible to selectively alpha-magnesiate a range of substrates, including Nmethylbenzimidazole, N-methyl triazole and pyrazine at room temperature (Figure
1a). Structural studies on the metallated intermediates (Figure 1b) provide important
clues that help to rationalise the stability of these species in solution.
Figure 1: a) Selective C2 metallation of pyrazine. b) Molecular structure of 2.
References:
[1] F. Chevallier, F. Mongin, Chem. Soc. Rev. 2008, 37, 595.
[2] S. E. Baillie, V. L. Blair, D. C. Blakemore, D. Hay, A. R. Kennedy, D. C. Pryde, E. Hevia, Chem.
Commun. 2012, 48, 1985.
[3] S. E. Baillie, V. L. Blair, T. D. Bradley, W. Clegg, J. Cowan, R. W. Harrington, A. Hernán-Gómez,
A. R. Kennedy, Z. Livingstone, E. Hevia, Chem. Sci., 2013, 4, 1895.
Poster presentation - P165
Towards new concepts for bond activation using an iron-PBP-pincer
complex
Lisa Vondung, Nicolas Frank, Dr. Robert Langer*
vondung@chemie.uni-marburg.de
Fachbereich Chemie, Philipps-Universität
Hans-Meerwein-Straße 4, 35032 Marburg
In the past, efficient homogeneous catalysts relied heavily on precious metals such as
ruthenium, platinum and palladium. An increasing demand for these metals has lead
to the wish of governments and industry to replace precious metal catalysts with more
abundant and ideally non-toxic metals. One highly attractive alternative is iron.[1]
Unfortunately, the established concepts can’t be easily transferred from ruthenium to
iron, as iron often prefers one electron redox processes over two electron processes.[2]
Thus the development of new concepts is required. The new iron-PBP-pincer complex
2 was obtained via formal BH3 insertion in a Fe-P bond (complex 1, see fig. 1)[3] and
subsequent rearrangement under CO atmosphere. The second reaction represents a
rare example of B-H activation of a BR4 species. Complexes 1 and 2 were
characterized by single crystal x-ray diffraction and NMR. NOESY-NMR
experiments revealed an exchange between the Fe-H and B-H in complex 2, which
was further investigated by temperature dependent NMR experiments and DFT
calculations. The Fe0L4-fragment, which is anticipated as an intermediate in the
exchange process has a high potential for bond activation.[4]
Figure 1. Synthesis of iron-PBP-pincer complex 2.
References:
[1] S. Enthaler, K. Junge, M. Beller, Angew. Chem. Int. Ed. 2008, 47, 3317-3321.
[2] P. J. Chirik, K. Wieghardt, Science 2010, 327, 794-795.
[3] N. Frank, K. Hanau, K. Flosdorf, R. Langer, Dalton Trans. 2013, 42, 11252-11261.
[4] (a) H.-F. Klein, S. Camadanli, R. Beck, D. Leukel, U. Flörke, Angew. Chem. Int. Ed. 2005, 44,
975-977. (b) R. Birk, H. Berke, G. Huttner, L. Zsolnai, Chem. Ber. 1988, 121, 1557-1564.
Poster presentation - P166
Trigonal to tetrahedral transitions in Cu(I) six-membered inorganic
true heterocycles
Michal Horni, Radim Binar and Marek Necas
michalh@mail.muni.cz
Department of Chemistry, Faculty of Science, Masaryk University
Kotlarska 267/2, 611 37 Brno
A series of six-membered Cu(I) true heterocycles[1] was prepared from reactions of
[Cu(PPh3)2]NO3 with Ph2P(S)-N-C(O)R {R = (CH2)3CH3, C6H5, C6H4F, C6H4Cl}
ligands. The synthesized compounds were characterized by 31P NMR spectroscopy
and single crystal X-ray diffraction. According to NMR spectroscopy, most of the
prepared complexes should contain copper in tetrahedral coordination environment.
After crystallization from CH2Cl2/hexane system, the complexes with PNC ligands
possessing dissimilar halogen substituent (position and type) on benzene ring show
different copper coordination polyhedra (Figure). Quantum chemical calculations are
undertaken to reveal thermodynamic and kinetic phenomena determining copper atom
coordination geometries.
Figure 1. Trigonal and tetrahedral Cu(I) complexes.
Acknowledgements: To Mr. Babiak and X-ray Diffraction and Bio-SAXS Core Facility, CEITEC
MU. European Regional Development Fund (CZ.1.05/1.1.00/02.0068).
References:
[1] Birdsall, D. J.; Green, J.; Ly, Q. T.; Novosad, J.; Necas, M.; Slawin, A. M. Z.; Woollins, J. D.; Zak,
Z., Eur. J. Inorg. Chem., 1999, 1445 – 1452.
Poster presentation - P167
The Transmetalation Strategy to Heterometallic Gold Clusters
Mathies V. Evers,(a) Arik Puls,(a) Christian Gemel,(a) Yuichi Negishi,(b) Roland A.
Fischer(a)*
Mathies.Evers@rub.de
(a) Chair of Inorganic Chemistry II, Ruhr-University Bochum
Universitätsstr. 150, 44801, Bochum (Germany)
(b) Department of Applied Chemistry, Faculty of Science, Tokyo University of Science
Shinjuku-ku, Tokyo, 162-8601 (Japan)
Gold clusters are prominent materials in nanoscience. They exhibit high reactivity,
catalytic activity and interesting optical properties, which are strongly dependent on
size, structure and capping ligands. Every cluster atom is crucial to the chemical and
physical features and thus, doping has evolved as a tool for the fine-tuning of the
properties. However, the established wet chemical synthesis (co-reduction) of
heterometallic clusters is challenging and limited in scope, especially if the nature of
the two metals is very different. Recently, we discovered a novel transmetalation
strategy to yield multiply metal-doped gold clusters: [M(AuPMe3)11(AuCl)]3+
(M@Au12, M = Ni, Pd, Pt) and [Mo(AuPMe3)8(GaCl2)3(GaCl)]+ (Mo@Au8Ga4) were
prepared from [M(GaCp*)4] and [Mo(GaCp*)6], respectively, by reaction with Cl–
Au–PMe3.[1] In expanding this concept we now discovered a unique access to the first
all-isonitrile-capped heterometallic gold clusters of the general formula
{[AuaMb]L12}2+ (L = CNtBu; M = Pd, Pt; a + b = 13). As shown by single-crystal
XRD and high resolution mass spectroscopy, their molecular structure consists of an
icosahedral metal cage with one central atom M and the other heterometal atoms M
distributed over the icosahedral shell. Interestingly, the electron count cve = 6 of the
obtained examples {[Au8M5]L12}2+ does not fit the Jellium superatom counting rules
for clusters.[2] The synthesis, spectroscopic features as well as molecular and
electronic structures will be discussed.
Figure 1. Synthesis of {[Au8M5](CNtBu)12}2+ (M = Pd, Pt) and mass spectrum for M = Pt.
References:
[1] A. Puls, P. Jerabek, W. Kurashige, M. Förster, M. Molon, T. Bollermann, M. Winter, C. Gemel, Y.
Negishi, G. Frenking, R. A. Fischer, Angew. Chem. Int. Ed., 2014, 53, 4327-4331.
[2] H. Häkkinen, Chem Soc. Rev., 2008, 37, 1847-1859.
Poster presentation - P168
Chiral Potassium Derivatives bearing Ligands of Natural Origin
María Fernández-Millán, Ghaita Chahboun, Jesús Cano, Tomás Cuenca and Marta E.
G. Mosquera
m.fernandezmillan@edu.uah.es
Departamento de Química Orgánica y Química Inorgánica, University of Alcalá
Ctra. Madrid-Barcelona Km. 33,600, E-28805, Alcalá de Henares (Madrid)
In this century, there has been a significant focus on the use of renewable feedstock as
raw materials to prepare chemicals. Renewable feedstock derived from plant-based
materials has also the advantage of presenting low toxicity. Moreover, the use of this
kind of natural occurring compounds is of particular interest as it permits to take
advantage of the pre-functionalization in those species. In this context, terpenoids are
molecules of great interest since they are starting materials of natural origin coming
from cheap non-food crops. In addition, they are chiral and commercially available as
enantiomerically pure products. As well, the presence of instaurations in their
structures gives the opportunity of performing further functionalization in a stereoselective way.[1] However, despite the great potential of terpene derivatives as ligands,
the number of coordination compounds with this type of species is low, especially
with main group metals. In our research group, we are interested in the preparation of
alkali derivatives with these ligands. This work has led us to the synthesis of
tetrametallic potassium chiral compounds very active in lactide polymerization
processes.
Figure 1. Terpene-based derivative.
References:
[1] A. J. D. Silvestre, A. Gandini en „Monomers, Polymers and Composites from Renewable
Resources“ Elsevier, 2008, 17-38.
K. Yao, C. Tang, Macromolecules 2013, 46, 1689-1712.
R. Noyori, M. Kitamura, Angew. Chem.-Int. Edit. Engl. 1991, 49;
K. R. Jain, W. A. Herrmann, F. E. Kuhn, Coord Chem. Rev. 2008, 252, 556.
Poster presentation - P169
PTFE (“Teflon”) Sealing Ring for greaseless conical Glass Joint and
for All-Glass-Syringe
Dietmar Glindemann, Uwe Glindemann
dglinde@aol.com
Glindemann Polymer Technologies
Goettinger Bogen 15, 06126 Halle
There is a prejudice that PTFE (“Teflon”) is too inelastic to be a hermetic sealant for
greaseless conical joints. Therefore, teaching books [1,2] recommend threaded or
flanged “O-ring joints” for hermetic manipulation of air- and moisture sensitive
chemicals if joint grease is no option. Here we show[3] that the common ground
conical glass joint can be sealed relatively hermetic and at low cost with a narrow flat
PTFE sealing ring (less than 1 mm wide and 0.1 mm thick, weight only 5 mg PTFE).
The sealing ring is high-vacuum tight (air leakage rate 10-8… 10-6 mBar*Liter/sec),
solvent tight (loss of ethyl acetate out of containers: 0.1 mg/day) and resistant to
fluctuation of temperature (freezing-thawing-heating cycles). The reusable PTFE
sealing ring prevents stuck joints, is thin enough to be used with all joint clamps and
is fixed elastically (without groove) on the glass joint. We demonstrate also that the
common all-glass-syringe (1-100 mL) becomes gastight by a similar exchangeable
sealing ring (PTFE) in a groove of the glass piston.[4]
Figure 1. Left: PTFE-sealing ring fixed elastic (no groove necessary). Middle: Sealing ring
intransparent without pressure. Right: Sealing ring transparent under sealing pressure. Far
right: A similar PTFE ring and a piston groove make an allglass-syringe.
References:
[1] D.F. Shriver, M.A. Drezdzon, The Manipulation of Air-Sensitive Compounds, Wiley: New York,
1986; p. 153-159.
[2] R.J. Errington, Advanced Practical Inorganic and Metalorganic Chemistry, Blackie; London, 1997,
p. 37-39.
[3] D. Glindemann, U. Glindemann, Fusion, 2001, 48, 29.
[4] D. Glindemann, All-glass syringe. Utility patent, DE 20 2006 020 555.1 (2009.03.05.).
Poster presentation - P170
Synthesis of Functional Inorganic Materials starting from Metal
Alkoxide and Metal Thiolate Precursors
Johannes Schläfer, Ufuk Atamtürk, Aida Jamil, Ralf Müller, Sanjay Mathur*
sanjay.mathur@uni-koeln.de
Institute of Inorganic Chemistry, University of Cologne
Greinstraße 6, D-50939 Cologne, Germany
Chemical synthesis of nanostructured materials starting from well-defined precursors
offers a high controllability over morphology as well as elemental composition and
purity. In order to meet the high requirements put on material performance
progressive processing techniques such as chemical vapor deposition were established
providing an elegant way to chemically assemble nanostructured phases starting from
molecular building units. Hereby, a drastically reduction of reaction parameters
during synthesis could be achieved by deploying single-source precursors providing a
high homogeneity already on a molecular level and exhibiting consistent
physicochemical properties such as vapor pressure or decomposition behavior. Metal
alkoxides and metal thiolates are a versatile class of precursors due to their unique
structural diversity, intrinsic propensity to hydrolysis, predefined M-E-bonds
(E = O, S) and defined decomposition mechanism. Here, we report the synthesis and
characterization of several homo- and heterometallic complexes and their deployment
as single-source precursor using different material synthesis approaches.1,2
Figure 1. SnO2 nanowires prepared by thermal CVD using alkoxide precursor [Sn(OtBu)4].
Acknowledgements: The authors gratefully acknowledge the financial support provided by the
University of Cologne.
References:
1 R. Müller, F. Hernandez-Ramirez, H. Shen, H. Du, W. Mader, S. Mathur, Chem. Mater. 2012, 24,
4028-4035.
2 J. Schläfer, S. Stucky, W. Tyrra, S. Mathur, Inorg. Chem. 2013, 52, 4002-4010.
Poster presentation - P171
Precursor Synthesis for the Generation of Fluorine-dope SnO2
Nanomaterials
Lisa Czympiel1, Corinna Hegemann1, Tim Heidemann1, Jean-Marius Lekeu1, Jan
Podhorsky2, Jiri Pinkas2, Sanjay Mathur1, *
sanjay.mathur@uni-koeln.de
1Institute of Inorganic Chemistry, University of Cologne
Greinstr. 6, D-50939, Cologne; 2Institute of Chemistry, Masaryk University Kamenice
753/5, 625 00 Brno
Fluorine-doped tin-dioxide (FTO) is a widely studied material for photo-catalysis, in
optical sensors or as thin film transparent electrode. The Research Group of Professor
Mathur is constantly investigating new precursors for a molecule-based approach to
nanomaterials by liquid-phase as well as gas-phase techniques. In the course of our
ongoing efforts towards suitable precursors we are investigating the properties of
heteroaryl alkenols as chelating ligands for various metals.[1] Through the direct
oxidation of tin (II) derivatives[2] as well as very atom economic solvent free melt
reactions dihalogeno tin(IV) bis(heteroarylalkenolates) are easily accessible.
Furthermore to optimize the tin to oxygen ratio for the later nanomaterial new
heteroleptic alkoxo Sn(IV) complexes were synthesized and characterized. These
compounds are interesting synthons for further chemical modifications or materials
syntheses.
Figure 1. Set of investigated potential molecular precursors for the synthesis of FTO.
Acknowledgements: The authors thank Dr. Wieland Tyrra for useful discussions and Dr. Stefan
Stucky for assistance with the X-ray crystal structure determination.
References:
[1] (a) . Brückmann, W. Tyrra, S. Stucky, S. Mathur, Inorg. Chem. 2012, 51, 3 − 2 (b) . Appel,
R. Fiz, W. Tyrra, S. Mathur, Dalton Trans. 2012, 41, 19 1−1990 (c) . Appel, J. Leduc, C. L.
Webster, J. W. Ziller, W. J. Evans, S. Mathur, Angew. Chem. Int. Ed. 2015, 54, 2209–2213; (d) L.
Czympiel, J. Pfrommer, W. Tyrra, M. Schäfer, S. Mathur, Inorg. Chem. 2015, 54, 25-37.
[2] (a) I. Giebelhaus, R. Müller, W. Tyrra, I. Pantenburg, T. Fischer, S. Mathur, Inorg. Chim. Acta
2011, 372, 3 0−3
(b) T. Heidemann, S. Mathur, Eur. J. Inorg. Chem. 2014, 506–510.
Poster presentation - P172
Exploring the Chemistry of Ternary Heterometallic Alkoxides
Corinna Hegemann, Tim Heidemann, Sanjay Mathur*
sanjay.mathur@uni-koeln.de
1Institute of Inorganic Chemistry, University of Cologne
Greinstr. 6, D-50939, Cologne
The bimetallic nonaalkoxo unit, {M2(OPri9)}-, is a promising building block to
rationally construct new heterobimetallic alkoxides[1] whereas no report is available
on the structural characterization of the {Ce2(OPri)9}- unit in the solid state. This
along with the interest for mixed-metal cerium containing ceramics prompted our
research work in heterobi- and trimetallic metal(IV)-isopropoxides. New
heterobimetallic halide isopropoxides of the general formula [IM{Ce2(OPri)9}]2(M =
Cd, Ba) were successfully used as synthons to novel ternary heterometal alkoxides
[{Cd(OPri)3}M{Ce2(OPri)9}]2
(M
=
Ba,
Sr)
and
the
monomeric
i
i
IV
i
IV
[{Al(OPr )4}(HOPr )Ba{M 2(OPr )9}] (M = Zr, Hf, Ce). Whereas the formation of
a heterotrimetallic framework in [{Cd(OPri)3}Ba{Ce2(OPri)9}]2 starting with
[ICd{Ce2(OPri)9}]2 involves the previously observed switching of cadmium and
alkaline earth metal atoms, [{Al(OPri)4}(HOPri)Ba{MIV2(OPri)9}] was obtained by a
straightforward salt elimination reaction between [ICd{MIV2(OPri)9}]2 and
[K{Al(OPri)3}]n [{Al(OPri)4}(HOPri)Ba{MIV2(OPri)9}] represents a novel structural
motif and the first example of a volatile homoleptic heterotrimetallic alkoxide
containing an trivalent metal atom.
Figure 1. Formation of the heterotrimetallic framework in [{Cd(OPri)3}Ba{Ce2(OPri)9}]2.
Acknowledgements: The authors thank Dr. Wieland Tyrra for useful discussions and Dr. Ingo
Pantenburg for assistance with the X-ray crystal structure determination.
References:
[1] a) M. Veith, S. Mathur, V. Huch, J. Chem. Soc., Dalton Trans. 1996, 12, 2485-2490; b) R. C.
Mehrotra, A. Singh, Polyhedron 1998, 17, 689-704; c) M. Veith, C. Mathur, S. Mathur, V. Huch,
Organometallics 1997, 16, 1292-1299; d) M. Veith, S. Mathur, V. Huch, Inorg. Chem. 1997, 36, 23912399; e) M. Veith, S. Mathur, C. Mathur, Polyhedron 1998, 17, 1005-1034; f) R. C. Mehrotra, A.
Singh, S. Sogani, Chem. Rev. 1994, 94, 1643-1660; g) K. G. Caulton, L. G. Hubert-Pfalzgraf, Chem.
Rev. 1990, 90, 969-995.
Poster presentation - P173
Ligand-Modulated Chemical and Structural Implications in
Aluminum Heteroaryl Alkenolates
Lisa Czympiel,(a) Mathias Schäfer,(b) Johannes Pfrommer,(a) Sanjay Mathur*(a)
sanjay.mathur@uni-koeln.de
a) Institute of Inorganic and b) Institute of Organic Chemistry, University of Cologne
Greinstr. 6, D-50939, Cologne
With continuing research interest and increasing technological importance of
nanomaterials, particularly thin films of functional materials, the quest for new
metal−organic compounds, enabling a controlled synthesis of new materials has
gained significant impetus in recent years. To study the mode of stabilization of the
triply charged aluminum ion by aromatic groups and heteroatoms like nitrogen,
oxygen, and sulfur, we report on a series of aluminum chelate complexes with six
different heteroaryl alkenolate anions. The chelating ability of the
NAr−CH−C(Rf)−OH backbone of the ligands and the stability of the resulting sixmembered ring offer an interesting option to limit the oligomerization of metal
complexes while simultaneously enhancing the volatility by incorporating an
perfluoralkyl-unit. Synthesis and characterization (gas phase, solution, and solid-state)
of a series of homoleptic and heteroleptic four‑, five- and six-fold coordinated
heteroaryl-alkenolato aluminum complexes were performed to demonstrate the
delicate interplay of structural and chemical influences of ligands in the design of new
precursors for chemical vapor deposition.
Figure 1. Correlation of coordination numbers of metal atoms in Al complexes with their
chemical shifts in 27Al NMR spectra.
Acknowledgements: Authors acknowledge G. Berden and J. Oomens for IRMPD-measurements, and
A.J.H.M. Meijer for theoretical calculations of the compounds which allowed the elucidation of gasphase structures.
References:
1 (a) L. Czympiel, J. Pfrommer, W. Tyrra, M. Schäfer, S. Mathur, Inorg. Chem., 2015, 54, 25 - 37; (b)
L. Brückmann, W. Tyrra, S. Mathur, G. Berden, J. Oomens, A.J.H.M. Meijer, M. Schäfer,
ChemPhysChem, 2012, 13, 2037 - 2045.
Poster presentation - P174
BODIPY-Cyclophosphazene-Fullerene Triad as Heavy Atom Free
Organic Triplet Photosensitizer
Elif OKUTAN*, Semiha YILDIRIM, Serkan YESILOT, Adem KILIC
eokutan@gtu.edu.tr
Department of Chemistry, Gebze Technical University
TR-41400, KOCAELI
Triplet photosensitizers have attracted much attention, because of their applications in
photovoltaics, photodynamic therapy (PDT) and the triplet-triplet annihilation photon
upconversions.[1] Generally the triplet photosensitizers are transition metal complexes
or the iodo/ bromo containing organic chromophores in which the heavy atom effect
facilitates ISC. Recently organic triplet photosensitizers based on BODIPY have been
reported.[2] But it is not always convenient to prepare iodinated/brominated organic
chromophore since the ISC property of these chromophores cannot be guaranteed. It
is still a challenge to design a heavy-atom-free organic triplet photosensitizer. In this
study, the synthesis and photophysical properties of new triad BODIPYcyclophosphazene-fullerene (Figure 1.) in which BODIPY moieties are connected to
an cyclophosphazene core, which acts as an thermally stable carrier/router and is
further linked to three C60 units. This model utilizes visible light absorbing three cis
directed BODIPY derivatives as antennas and cis directed fullerenes as spin convertor
in the same molecule. This molecular design can trigger the strong absorption of
visible light and very long-lived triplet excited states and may be used as heavy atom
free organic triplet photosentisitizers.
Acknowledgements: The authors would like to thank the Scientific and Technical Research Council of
Turkey for financial support TUBITAK (Grant 114Z763 )
References:
[1] W. Wu, H. Guo, W. Wu, S. Ji, J. Zhao, J. Org. Chem.,2011, 76, 70 −70 .
[2] S. Ji, W. Wu , W. Wu, H. Guo, J. Zhao, Angew. Chem., Int. Ed., 2011, 50, 1 2 −1 29.
Poster presentation - P175
List of Participants
Dr. Tomohiro Agou
Institute for Chemical Research, Kyoto
University
6110011 Kyoto
Japan
Mr. Frederik Aicher
72119 Ammerbuch
Germany
Ms. Nazmiye Akbay Kilic
Gebze Technical University
41400 Kocaeli
Turkey
Ms. Mansura Akter
53117 Bonn
Germany
Ms. Lena Albers
Universität Oldenburg
26129 Oldenburg
Germany
Prof. Simon Aldridge
University of Oxford
OX1 3QR Oxford
United Kingdom
Prof. Chris Allen
University of Vermont
05405 Burlington
United States
Martina Amann
University of Regensburg
93053 Regensburg
Germany
Mr. Naoki Ando
Nagoya University
4648602 Nagoya
Japan
Mr. Marius Arz
University of Bonn
53121 Bonn
Germany
Bernhard Baars
University of Bonn
53123 Bonn
Germany
Katharina Baier
University of Regensburg
93053 Regensburg
Germany
Mr. Matthew Baker
ETH Zürich
8049 Zürich
Switzerland
Prof. Maravanji Balakrishna
I I T BOMBAY
400076 Mumbai
India
Dr. Gábor Balázs
University of Regensburg
93053 Regensburg
Germany
Mr. Hung Banh
Ruhr-Universität Bochum, AC II
44801 Bochum
Germany
List of Participants
Mr. Peter Bartoš
Masaryk University
971 01 Prievidza
Slovakia
Dr. Heiko Bauer
Friedrich-Alexander University ErlangenNürnberg
91058 Erlangen
Germany
Dr. Thomas Baumgartner
University of Calgary, Department of
Chemistry
T2N 1N4 Calgary
Canada
Dr. Michael Beckett
Bangor University
LL57 2UW Bangor
United Kingdom
Prof. Jens Beckmann
Universität Bremen
28334 Bremen
Germany
Ms. Imtiaz Begum
University of Bonn
53119 Bonn
Germany
Mr. Lukas Belter
40468 Düsseldorf
Germany
Dr. Zoltán Benkö
Budapest University of Technology and
Economics
1111 Budapest
Hungary
Prof. Louise Berben
University of California Davis
95616 Davis
United States
Prof. Guy Bertrand
UC San Diego
CA 92093 San Diego
United States
Prof. Serap Beşli
Gebze Technical University
41400 OCAE İ
Turkey
Prof. Holger Bettinger
Institute for Organic Chemistry, University
Tuebingen
72076 Tuebingen
Germany
Dr. Ilya Bezkishko
IOPC KSC RAS
42088 Kazan
Russia
Mr. Michal Bílek
University od Pardubice
532 10 Pardubice
Czech Republic
Mr. Justin Frank Binder
Department of Chemistry and Biochemistry,
University of Windsor
N9B 3P4 Windsor
Canada
Mr. Markus Blum
University of Stuttgart
73614 Schorndorf
Germany
Dr. Michael Bodensteiner
University of Regensburg
93053 Regensburg
Germany
Prof. René Boeré
University of Lethbridge
T1K3M4 Lethbridge
Canada
List of Participants
Dr. Tobias Boettcher
Albert-Ludwigs Universität Freiburg
79104 Freiburg
Germany
Mr. Jaap E. Borger
VU University Amsterdam
1081HV Amsterdam
Netherlands
Mr. Stefan Borucki
University of Kassel
34132 Kassel
Germany
Mr. Jiří Böserle
Univerzita Pardubice
53210 Pardubice
Czech Republic
Dr. Didier Bourissou
Paul Sabatier University
31062 Toulouse
France
Jens Braese
University of Regensburg
93053 Regensburg
Germany
Helena Brake
University of Regensburg
93053 Regensburg
Germany
Prof. Holger Braunschweig
Julius-Maximilians-Universität Würzburg
97074 Würzburg
Germany
Prof. Frank Breher
Karlsruhe Institute of Technology (KIT),
Institute of Inorganic Chemistry
76131 Karlsruhe
Germany
Dr. Nora Breit
Technische Universität Berlin
10623 Berlin
Germany
Mr. Jonas Bresien
University of Rostock
18059 Rostock
Germany
Dr. Lies Broeckaert
Universität Marburg
35032 Marburg
Germany
Natalie Brüll
Philipps-Universität Marburg
35039 Marburg
Germany
Prof. Neil Burford
University of Victoria
V8W 3V6 Victoria
Canada
Mr. Philipp Büschelberger
University of Regensburg
93040 Regensburg
Germany
Dr. Jesus Campos Manzano
University of Oxford
OX1 3QR Oxford
United Kingdom
Ms. Elif Busra Celebi
Yildiz Technical University
34220 istanbul
Turkey
Dr. Uttam Chakraborty
University of Regensburg
93055 Regensburg
Germany
List of Participants
Dr. Yuk Chi Chan
Nanyang Technological University
637371 Singapore
Singapore
Ms. Bronte Charette
R2J 0B4 Winnipeg
Canada
Prof. Ching-Wen Chiu
National Taiwan University
10617 Taipai
Taiwan
Prof. Tristram Chivers
University of Calgary
T2N 1N4 Calgary, Alberta
Canada
Mr. Tomas Chlupaty
University of Pardubice
53210 Pardubice
Czech Republic
Prof. John Corrigan
The University of Western Ontario
N6A5B7 London
Canada
Dr. Michael Cowley
School of Chemistry, University of
Edinburgh
EH9 3FJ Edinburgh
United Kingdom
Prof. Christopher C. Cummins
Massachusetts Institute of Technology
MA 02139 Cambridge
United States
Dr. Derya Davarci
Gebze Technical University
41400 OCAE İ
Turkey
Dr. Andrew Davies
Bangor University
LL57 2UW Bangor
United Kingdom
Laia Davin
University of Strathclyde
G1 1XL Glasgow
United Kingdom
Prof. Stefanie Dehnen
FB Chemie, Philipps-Universität Marburg
35039 Marburg
Germany
Dr. Fabian Dielmann
University of Münster
48149 Münster
Germany
Ms. Katharina Dilchert
Ruhr-Universität Bochum
44809 Bochum
Germany
Dr. Adinarayana Doddi
Technische Universität Braunschweig
38106 Braunschweig
Germany
Mr. Carsten Donsbach
Philipps-University Marburg
D-35032 Marburg
Germany
Mr. Eike Dornsiepen
Philipps-Universität Marburg
35039 Marburg
Germany
Dr. Libor Dostál
University of Pardubice
53210 Pardubice
Czech Republic
List of Participants
Prof. Ralf Dr. Steudel
14055 Berlin
Germany
Dr. Jonathan Dube
Max Planck Institut für Kohlenforschung
45470 Mülheim an der ruhr
Germany
Luis Duetsch
University of Regensburg
93053 Regensburg
Germany
Ms. Klara Edel
University of Tübingen
72076 Tübingen
Germany
Ms. Jessica Edrich
71069 Sindelfingen
Germany
Dr. Andreas Ehlers
Vrije Univeriteit
1081HV Amsterdam
Netherlands
Mr. Carsten Eisenhut
Technische Universität Berlin
10623 Berlin
Germany
Dr. Mehdi Elsayed Moussa
University of Regensburg
93049 Regensburg
Germany
Mr. Armin Rainer Eulenstein
Philipps-Universität Marburg
35032 Marburg
Germany
Mr. Mathies Evers
Ruhr-University Bochum
45468 Mülheim an der Ruhr
Germany
Dr. Rosalyn Falconer
University of Bristol
BS8 1TS Bristol
United Kingdom
Mr. Jan Faßbender
53639 Königswinter
Germany
Prof. Thomas Fässler
Technische Universität München
85748 Garching
Germany
Dr. María Fernández Millán
University of Alcalá
28871 Alcalá de Henares (Madrid)
Spain
Prof. Roland C. Fischer
TU Graz
8010 Graz
Austria
Martin Fleischmann
University of Regensburg
93051 Regensburg
Germany
Dr. Daniel Franz
Technische Universität Berlin
10623 Berlin
Germany
Dr. Kerstin Freitag
Ruhr-Universität Bochum
44801 Bochum
Germany
List of Participants
Prof. Francois Gabbai
Texas A&M University
TX 77843 College Station
United States
Dr. Olga Gapurenko
Institute of Physical and Organic Chemistry,
Southern Federal University
344090 Rostov on Don
Russia
Mr. Francisco Miguel García-Valle
University of Alcalá
28871 Alcalá de Henares
Spain
Prof. Derek P. Gates
University of British Columbia
V6T 1Z1 Vancouver
Canada
Eugenie Geringer
Philipps-Universität Marburg
35032 Marburg
Germany
Mr. Priyabrata Ghana
University of Bonn
53121 Bonn
Germany
Dr. Robert Gilliard
ETH Zurich
8093 Zurich
Switzerland
Dr. Glen Briand
Mount Allison University
E4L1G8 Sackville, New Brunswick
Canada
Dr. Dietmar Glindemann
Glindemann PTFE Sealing Rings
D-06126 Halle
Germany
Prof. Jose Goicoechea
University of Oxford
OX1 3TA Oxford
United Kingdom
Mr. Christopher Golz
TU Dortmund, Anorganische Chemie
44227 Dortmund
Germany
Dr. Marta Elena Gonzalez Mosquera
Universidad de Alcala
28805 Alcala de Henares
Spain
Mr. Paul Gray
University of Victoria
V8P4R2 Victoria
Canada
Ms. Christa Grogger
TU Graz
8010 Graz
Austria
Mr. Henning Großekappenberg
Universität Oldenburg
26129 Oldenburg
Germany
Mr. Peter Grüninger
University of Tübingen
72762 Reutlingen
Germany
Prof. Hansjörg Grützmacher
ETH Zürich
8093 Zürich
Switzerland
Prof. Dietrich Gudat
University of Stuttgart
70550 Stuttgart
Germany
List of Participants
Mr. Lukas Guggolz
Philipps-Universität Marburg
35043 Marburg
Germany
Mr. Michael Haas
Institute of Inorganic Chemistry
8010 Graz
Austria
Prof. Ferda Hacivelioglu
Gebze Technical University
41400 Kocaeli
Turkey
Ms. Katharina Hanau
Philipps-Universität Marburg
35032 Marburg
Germany
Ms. Róża Hamera
University of Lodz, Faculty of Chemistry,
Department of Organic and Applied
Chemistry
91-403 Łódź
Poland
Ms. Kerstin Hansen
Technische Universität Berlin
10623 Berlin
Germany
Prof. Sjoerd Harder
University Erlangen-Nürnberg
91058 Erlangen
Germany
Ms. Khatera Hazin
UBC
V3J7G8 Burnaby
Canada
Dr. Corinna Hegemann
University of Cologne
50939 Cologne
Germany
Oliver Hegen
University of Regensburg
93053 Regensburg
Germany
Mr. Tim Heidemann
50937 Köln
Germany
Dr. Dominikus Heift
LPCNO, INSA Toulouse
31077 Toulouse
France
Claudia Heindl
University of Regensburg
93051 Regensburg
Germany
Dr. Johanna Heine
Philipps-Universität Marburg
35043 Marburg
Germany
Mr. Martin Hejda
University od Pardubice
53210 Pardubice
Czech Republic
Dr. Holger Helten
RWTH Aachen University
52056 Aachen
Germany
Mr. Dirk Herrmann
University of Regensburg
93053 Regensburg
Germany
Prof. Eva Hevia
University of Strathclyde
G1 1XQ Glasgow
United Kingdom
List of Participants
Prof. Evamarie Hey-Hawkins
Universität Leipzig
04103 Leipzig
Germany
Dr. Daniel Himmel
Krossing Group, Freiburg
79098 Freiburg im Breisgau
Germany
Mr. Alexander Hinz
Universität Rostock
18059 Rostock
Germany
Sandra Hitzel
University of Kassel
34132 Kassel
Germany
Mr. Michal Horni
Masaryk University
61137 Brno
Czech Republic
Mr. Emanuel Hupf
Universität Bremen
28359 Bremen
Germany
Prof. Takeaki Iwamoto
Tohoku University
9808578 Sendai
Japan
Dr. Roman Jambor
University of Pardubice
53210 Pardubice
Czech Republic
Ms. Aida Jamil
University of Cologne
50939 cologne
Germany
Dr. Brian Johnson
Wiley-VCH
69469 Weinheim
Germany
Prof. Cameron Jones
Monash University
VIC 3800 Clayton
Australia
Charlotte Jones
Bangor University
LL57 2UW Bangor
United Kingdom
Mr. Maximilian Jost
Philipps-Universität Marburg
35032 Marburg
Germany
Mr. Philip Junker
University of Bonn
53115 Bonn
Germany
Mr. Andrew Jupp
University of Oxford
OX13PN Oxford
United Kingdom
Dr. Titel Jurca
University of Bristol
BS8 1TS Bristol
United Kingdom
Prof. Klaus Jurkschat
Fakultät für Chemie und Chemische
Biologie,TU Dortmund
44221 Dortmund
Germany
Tobias Kahoun
University of Regensburg
93053 Regensburg
Germany
List of Participants
Prof. Wolfgang Kaim
University of Stuttgart
70550 Stuttgart
Germany
Mr. Manuel Kapitein
Philipps-Universität Marburg
35043 Marburg
Germany
Mr. Denis Kargin
Universität Kassel
34471 Volkmarsen
Germany
Mr. Surendar Karwasara
Indian Institute of Technology Delhi
110016 Delhi
India
Mr. Ralf Kather
Universität Bremen
28359 Bremen
Germany
Mr. Dominik Keiper
Philipps-Universität Marburg
35032 Marburg
Germany
Mr. Zsolt Kelemen
Budapest University of Technology and
Economics
H-1111 Budapest
Hungary
Dr. Shabana Khan
Indian Institute For Science Education And
Research Pune, India
411008 PUNE
India
Ms. Sabrina Khoo
Nanyang Technological University
419593 Singapore
Singapore
Karin Kilgert
University of Regensburg
93053 Regensburg
Germany
Mr. Andreas Kirchmeier
University of Kassel
34132 Kassel
Germany
Ms. Melina Klein
University of Bonn
53121 Bonn
Germany
Dr. Evgeny Kolychev
University of Oxford
OX1 3TA Oxford
United Kingdom
Prof. Sergey Konchenko
Nikolaev Institute of Inorganic Chemistry SB
RAS
630090 Novosibirsk
Russia
David Konieczny
University of Regensburg
93053 Regensburg
Germany
Dr. Jari Konu
University of Jyväskylä
FI-40014 Jyväskylä
Finland
Stephanie Kosnik
University of Windsor, Chemistry &
Biochemistry
N9G2L7 Windsor
Canada
Barbara Krämer
University of Regensburg
93053 Regensburg
Germany
List of Participants
Mr. Kilian Krebs
University of Tübingen
72076 Tübingen
Germany
Dr. Robert Kretschmer
University of Regensburg
93053 Regensburg
Germany
Ms. Ulrike Kroesen
TU Dortmund, Anorganische Chemie
44227 Dortmund
Germany
Prof. Ingo Krossing
Uni Freiburg
79104 Freiburg i. Br.
Germany
Mr. Selva Kumar
642005 coimbatore
India
Dr. Arvind Kumar Gupta
NDHU
97401 Hualien
Taiwan
Mr. Mahendra Kumar Sharma
Iit Delhi, India
110016 NEW DELHI
India
Dr. Oleksandr Kysliak
University of Tübingen
72074 Tübingen
Germany
Mr. René Labbow
University of Rostock
18059 Rostock
Germany
Giuliano Lassandro
University of Regensburg
93053 Regensburg
Germany
Dr. Richard Layfield
School of Chemistry, The University of
Manchester
M13 9PL Manchester
United Kingdom
Lucia-Myongwon Lee
McMaster University
L8S4M1 Hamilton
Canada
Dr. Vladimir LEE
University of Tsukuba
305-8571 Tsukuba
Japan
Mr. Otfried Lemp
Philipps-Universität Marburg
35032 Marburg
Germany
Dr. Christophe Lescop
Institut des Sciences Chimiques de Rennes
35042 Rennes
France
Ms. Eliza Leusmann
Philipps-Universität Marburg
35032 Marburg
Germany
Mr. Niels Lichtenberger
Philipps University of Marburg
35043 Marburg
Germany
Dr. H. Bernhard Linden
Linden CMS GmbH
28844 Weyhe
Germany
List of Participants
Mr. Mathias Linden
Linden CMS GmbH
28844 Weyhe
Germany
Dr. Felicitas Lips
University of Muenster
48149 Münster
Germany
Prof. Chen-Wei Liu
National Dong Hwa University
97401 Hualien
Taiwan
Mr. Siu Kwan Lo
University of Oxford
OX1 3TA Oxford
United Kingdom
Ms. Alicia López Andarias
Organisch-Chemisches Institut
69115 Heidelberg
Germany
Ms. Kathrin Louven
TU Dortmund, Anorganische Chemie
44227 Dortmund
Germany
Petra Lugauer
University of Regensburg
93053 Regensburg
Germany
Mr. Dennis Lutters
Universität Oldenburg
26129 Oldenburg
Germany
Dr. Charles Macdonald
University of Windsor, Chemistry &
Biochemistry
N9B 3P4 Windsor, Ontario
Canada
Eric Mädl
University of Regensburg
93051 Regensburg
Germany
Dr. Alexander Makarov
Novosibirsk Institute Of Organic Chemistry
630090 Novosibirsk
Russia
Dr. Payal Malik
Institut für Anorganische Chemie, Uni-Bonn
D-53121 Bonn
Germany
Prof. Ian Manners
University of Bristol
BS8 1TS Bristol
United Kingdom
Christian Marquardt
University of Regensburg
93053 Regensurg
Germany
Mr. David Martin
CNRS Université Joseph Fourier
BP53 38041 Grenoble cedex 9
France
Prof. Pradeep Mathur
I.I.T. Indore
452020 Indore
India
Dr. Rebecca Melen
Cardiff University
CF10 3AT Cardiff
United Kingdom
Daniela Meyer
University of Regensburg
93053 Regensburg
Germany
List of Participants
Mr. Stefan Mitzinger
Philipps-Universität Marburg
35043 Marburg
Germany
Prof. Grzegorz Mloston
Faculty of Chemistry, University of Lodz
91-403 Lodz
Poland
Mr. Dennis Mo
40591 Duesseldorf
Germany
Moritz Modl
University of Regensburg
93053 Regensburg
Germany
Dr. Heather Montgomery
Royal Society of Chemistry
CB4 0WF Cambridge
United Kingdom
Fabian Mueller
ETH Zürich
8093 Zurich
Switzerland
Julian Müller
University of Regensburg
93053 Regensburg
Germany
Prof. Thomas Müller
CvO Universität Oldenburg
26129 Oldenburg
Germany
Prof. Robert E. Mulvey
University of Strathclyde
G1 1XQ Glasgow
United Kingdom
Dr. María Teresa Muñoz-Fernández
University Of Alcalá
28871 Alcalá De Henares (Madrid)
Spain
Ms. Cristina Murcia García
University of Bonn
53123 Bonn
Germany
Prof. Ramaswamy Murugavel
400076 Mumbai
India
Ms. Ceylan Mutlu
Gebze Technical University
41400 Kocaeli
Turkey
Mr. Koichi Nagata
Kyoto university
611-0011 Uji city
Japan
Mr. Dominik Naglav
45141 Essen
Germany
Mr. David Nieder
Saarland University
66125 Saarbrücken-Dudweiler
Germany
Mr. Miroslav Novák
University od Pardubice
53210 Pardubice
Czech Republic
Isabell Nußbruch
Philipps-Universität Marburg
35032 Marburg
Germany
List of Participants
Prof. Laszlo Nyulaszi
Budapest University of Technology and
Economics
H-1111 Budapest
Hungary
Mr. Tatsumi Ochiai
Technische Universität Berlin
10623 Berlin
Germany
Mr. Jan Oetzel
University of Kassel
34132 Kassel
Germany
Dr. Elif OKUTAN
Gebze Technical University
41400 KOCAELI
Turkey
Dr. Roman Olejník
University of Pardubice
CZ 532 10 Pardubice
Czech Republic
Prof. Iwao Omae
Omae Research Laboratories
350-1317 Sayama, Saitama
Japan
Ms. Isabell Omlor
Saarland University
66280 Sulzbach
Germany
Dr. Timo Ott
47169 Duisburg
Germany
Mr. Jürgen Pahl
FAU Erlangen-Nürnberg
91058 Erlangen
Germany
Dr. Eugenia Peresypkina
University of Regensburg
93053 Regensburg
Germany
Prof. Rudolf Pietschnig
University of Kassel, Institut für Chemie und
CINSaT
34132 Kassel
Germany
Prof. Philip P. Power
UC Davis
CA 95616 Davis
United States
Prof. Paul Pringle
University of Bristol
BS8 1TS Bristol
United Kingdom
Dr. Nikolay Pushkarevsky
Nikolaev Institute of inorganic chemistry
630090 Novosibirsk
Russia
Dr. Boomi Shankar Ramamoorthy
Indian Institute of Science Education and
Research, Pune
411008 Pune
India
Mr. Crispin Reinhold
Universität Oldenburg
26129 Oldenburg
Germany
Ms. Kirsten Reuter
Philipps-Universität Marburg
35037 Marburg
Germany
Mr. Tomáš Řičica
University od Pardubice
53210 Pardubice
Czech Republic
List of Participants
Felix Riedlberger
University of Regensburg
93053 Regensburg
Germany
Mr. Benjamin Ringler
Philipps-Universität Marburg
35032 Marburg
Germany
Mr. Niklas Rinn
Philipps University Marburg
35039 Marburg
Germany
Dr. Arnab Rit
University of Oxford
OX1 3TA Oxford
United Kingdom
Prof. Jamie Ritch
Department of Chemistry, The University of
Winnipeg
R3B 2E9 Winnipeg
Canada
Prof. Eric Rivard
University of Alberta
AB T6G Edmonton
Canada
Mr. Andrew Roberts
University of Strathclyde
G1 1XQ Glasgow
United Kingdom
Dr. Thomas Robinson
University of Oxford
OX1 3TA Oxford
United Kingdom
Prof. Greg Robinson
University of Georgia
GA 30602 Athens
United States
Mr. Christian Roedl
University of Regensburg
93040 Regensburg
Germany
Dr. Carlos Romero-Nieto
Organisch-Chemisches Institut
69120 Heidelberg
Germany
Eva-Maria Rummel
University of Regensburg
93053 Regensburg
Germany
Reinhard Rund
University of Regensburg
93053 Regensburg
Germany
Dr. Chris Russell
University of Bristol
BS8 1TS Bristol
United Kingdom
Prof. Ales Ruzicka
University of Pardubice
53210 Pardubice
Czech Republic
Prof. Masaichi Saito
Department of Chemistry, Saitama
University
338-8570 Saitama
Japan
Silke Santner
Philipps-Universität Marburg
35032 Marburg
Germany
Prof. Takahiro Sasamori
Kyoto University
611-0011 Uji, Kyoto
Japan
List of Participants
Prof. Manfred Scheer
University of Regensburg
93053 Regensburg
Germany
Prof. David Scheschkewitz
Saarland University
66125 Saarbrücken
Germany
Dr. Johannes Schläfer
University of Cologne
50939 Cologne
Germany
Monika Schmidt
University of Regensburg
93053 Regensburg
Germany
Mr. Dominik Schnalzer
Graz University of Technology
8042 Graz
Austria
Ms. Julia Schneider
University of Tübingen
72076 Tübingen
Germany
Prof. Andreas Schnepf
University of Tübingen
72076 Tübingen
Germany
Thomas Schottenhammer
University of Regensburg
93053 Regensburg
Germany
Andrea Schreiner
University of Regensburg
93053 Regensburg
Germany
Mr. Jan Schroeder
79108 Freiburg
Germany
Prof. Axel Schulz
Universität Rostock
18059 Rostock
Germany
Ms. Miriam Schwab
University of Freiburg
79100 Freiburg
Germany
Mr. Kai Schwedtmann
Technische Universität Dresden
01062 Dresden
Germany
Dr. Michael Seidl
University of Regensburg
93051 Regensburg
Germany
Andreas Seitz
University of Regensburg
93053 Regensburg
Germany
Dr. Nikolay Semenov
Novosibirsk Institute of Organic Chemistry
630090 Novosibirsk
Russia
Dr. Elif Şenkuytu
Gebze Technical University
41400 Kocaeli
Turkey
Kamna Sharma
400076 Mumbai
India
List of Participants
Prof. Ulrich Siemeling
University of Kassel
34132 Kassel
Germany
Mr. Christian Sindlinger
University of Tübingen
72076 Tübingen
Germany
Prof. Nanhai Singh
Banaras Hindu University
221005 Varanasi
India
Mr. Jatinder Singh
Iit Delhi, India
110016 New Delhi
India
Prof. Alexandra Slawin
University of St Andrews
KY16 9ST St Andrews
United Kingdom
Dr. Olivia Sleator
Rigaku Europe
TN15 6QY Sevenoaks
United Kingdom
Dr. Chris Slootweg
VU University Amsterdam
1081 HV Amsterdam
Netherlands
Prof. Cheuk-Wai So
Nanyang Technological University
637371 Singapore
Singapore
Fabian Spitzer
University of Regensburg
93051 Regensburg
Germany
Prof. Dietmar Stalke
Georg-August Universität
37077 Göttingen
Germany
Andreas Stauber
University of Regensburg
93053 Regensburg
Germany
Dr. Tom Stennett
Universität Erlangen-Nürnberg
91058 Erlangen
Germany
Prof. Doug Stephan
University of Toronto
M5S 3H6 Toronto
Canada
Prof. Rainer Streubel
University of Bonn
53121 Bonn
Germany
Prof. Carsten Strohmann
TU Dortmund
44227 Dortmund
Germany
Prof. Harald Stueger
Graz University of Technology
A8010 Graz
Austria
Mr. Tomohiro Sugahara
Institute for Chemical Research, Kyoto Univ.
611-0011 Uji, Kyoto
Japan
Mr. Riccardo Suter
ETH Zurich
8005 Zürich
Switzerland
List of Participants
Dr. Petr Svec
University of Pardubice
CZ-53210 Pardubice
Czech Republic
Prof. Claire Tessier
University of Akron
44325-3601 Akron, Ohio
United States
Dr. Günther Thiele
Philipps-Universität Marburg
35043 Marburg
Germany
Prof. Alexey Timoshkin
St. Petersburg State University
198504 St. Petersburg
Russia
Prof. Norihiro Tokitoh
Institute for Chemical Research, Kyoto
University
611-001 Uji, Kyoto
Japan
Dr. Yasemin Tümer
78050 Karabük
Turkey
Dr. Jan Turek
ALGC, Department of Chemistry, Faculty of
Sciences, Free University of Brussels
1050 Brussels
Belgium
Prof.. Werner Uhl
University of Muenster
48149 Münster
Germany
Mr. Fabian Uhlemann
University of Tuebingen
72147 Nehren
Germany
Prof. Frank Uhlig
Graz University of Technology
8010 Graz
Austria
Prof. Aylin Uslu
Gebze Technical University
41400 Kocaeli
Turkey
Mr. Leon van der Boon
VU University Amsterdam
1081 HV Amsterdam
Netherlands
Prof. Ignacio Vargas-Baca
McMaster University
L8S 4M1 Hamilton
Canada
Dr. Preeti Vashi
Wiley-VCH, European Journal of Inorganic
Chemistry
69469 Weinheim
Germany
Valentin Vass
University of Regensburg
93053 Regensburg
Germany
Prof. Michael Veith
Universität des Saarlandes und INM
66123 Saarbrücken
Germany
Dr. Alexander Virovets
University of Regensburg
93053 Regensburg
Germany
Dr. Matthias Vogt
Universität Bremen
28359 Bremen
Germany
List of Participants
Prof. Carsten von Hänisch
Philipps-Universität Marburg
35032 Marburg
Germany
Ms. Lisa Vondung
Philipps-Universität Marburg
35032 Marburg
Germany
Mr. Jan Vrána
Univerzita Pardubice
53210 Pardubice 2
Czech Republic
Ms. Iva Vránová
Univerzita Pardubice
53210 Pardubice 2
Czech Republic
Prof. Rory Waterman
University of Vermont
05401 Burlington
United States
Mr. Jordan Waters
University of Oxford
OX1 3TA Oxford
United Kingdom
Prof. Jan J. Weigand
Technische Universität Dresden
01062 Dresde
Germany
Dr. Bastian Weinert
Philipps-Universität Marburg
35037 Marburg
Germany
Rudolf Weinzierl
University of Regensburg
93053 Regensburg
Germany
Mr. Stefan Weller
University of Stuttgart
74427 Fichtenberg
Germany
Prof. Lars Wesemann
University of Tübingen
72076 Tübingen
Germany
Ms. Jana Weßing
Ruhr-Universität Bochum, Lehrstuhl für
Anorganische Chemie II
44801 Bochum
Germany
Prof. Robert West
University of Wisconsin-Madison
53706-1396 Madison
United States
Mr. Philipp Willmes
Saarland University
66125 Saarbrücken-Dudweiler
Germany
Dr. Robert Wilson
Philipps-Universität Marburg
D-35032 Marburg
Germany
Prof. Robert Wolf
University of Regensburg
D-93040 Regensburg
Germany
Prof. J Derek Woollins
University of St Andrews
KY16 9ST St Andrews
United Kingdom
Dr. Ronald Wustrack
Universität Rostock
18059 Rostock
Germany
List of Participants
Mr. Dhirendra Yadav
110016 new delhi
India
Prof. Shigehiro Yamaguchi
Nagoya University
464-8602 Nagoya
Japan
Prof. Yohsuke Yamamoto
Hiroshima University
739-8526 Higashi-Hiroshima
Japan
Mr. Cem Burak Yildiz
Saarland University
66125 Saarbrücken-Dudweiller
Germany
Mr. Sivathmeehan Yogendra
Technische Universität Dresden
01162 Dresden
Germany
Ms. Hui Zhao
Saarland University
66125 Saarbrucken
Germany
Prof. Andrey Zibarev
Russian Academy of Sciences, Novosibirsk
Institute of Organic Chemistry
630090 Novosibirsk
Russia
Harmen Zijlstra
University of Erlangen-Nürnberg
91058 Erlangen
Germany
List of Participants