ADVANCED CATALYSIS:
BIOMIMETIC OXIDATION
CATALYSIS
Maria Louloudi
Lab of Inorganic Chemistry
Department of Chemistry,
University of Ioannina,
45110 Ioannina,
GREECE
Oxidation of hydrocarbons
?
R1 C C R4
R2 R3
oxidant
catalyst
O
R1 C C R 4
R2 R3
H2 H2
R1 C C R2
oxidant
catalyst
H2 OH
R1 C C R2
H
H2 H2
R1 C C R2
oxidant
catalyst
H2 O
R1 C C R2
?
Phenol oxidation
OH
OH
C-(CH3)3
O2
HO
O
C-(CH3)3
catalyst
C-(CH3)3
2,4-di-t-butylphenol
DTBP
O2
O
C-(CH3)3
catalyst
C-(CH3)3
3,5-di-t-butylcatechol
DTBC
C-(CH3)3
3,5-di-t-butylquinone
DTBQ
Fine chemistry
&
Industry
DEMAND: EFFICIENT CATALYSTS FOR SELECTIVE
OXIDATION OF HYDROCARBONS UNDER MILD
CONDITIONS
alkane oxidation
(i.e., CH4  CH3OH,
steroid hydroxylation)
olefin oxidation
Oxidation-degradation of environmental pollutant
(i.e., chlorophenol degradation)
New oxidation catalysts
ENERGY SAVING STRATEGIES
Catalytic reactions
Environmental friendly oxidants
Biomimetic Systems
Heterogeneous Catalysts
TYPES OF CATALYSTS - ENZYMES
•
The “Gold Standard” of catalysts
•
Highly specific
•
Highly selective
•
Highly efficient
•
Catalyze very difficult reactions
–
–
•
N2  NH3
CO2 + H2O  C6H12O6
Works better in a cell than in a 100000 l reactor
MANGANESE CATALASE
2 H2O2
ÊáôáëÜóç
Core of the active site
in Lactobacillus plantarum catalase.
2 H2O
+ O2
Proposed mechanism of H2O2
decomposition by manganese catalase
Wu, A. J.; Penner-Hahn, J. E.; Pecoraro, V. L., Chem. Rev. 2004, 104, 903-938
MANGANESE CATALASE MIMICS
Structures of some of the ligands used for manganese catalase mimics
MANGANESE SUPEROXIDE DISMUTASE (MN-SOD)
The active center of
Manganese Superoxide Dismutase
Superoxide dismutation mechanism for
mononuclear Mn-SOD under physiological
conditions
Holm, R. H.; Kennepohl, P.; Solomon, E. I., Chem. Rev. 1996, 96, 2239-2314
MANGANESE SOD MIMICS
Structures of some of the ligands used in the synthesis of Mn complexes and manganese
complexes for modeling of MnSOD
P-450
Active site of P-450 (X = H2O or OH–)
Generally accepted mechanism of
Catalytic cycle of P-450
Mansuy, D.; Battioni, P., in Bioinorganic catalysis, Reedijk, J.; Bouwman, E. Ed; Second
Edition, Marcel Deker, New York, 1999; pp 323-354
METHANE MONOOXYGENASE (MMO)
CH4 + O2 + NADH + H+
CH3OH + H2O + NAD+
Active site structures of MMOox and MMOred
Wallar, B. J.; Lipscomb, J. D., Chem. Rev. 1996, 96, 2625-2657
Generally accepted mechanism of Catalytic cycle of MMO
BLEOMYCIN
Schematic representation of the structure of a part of iron bleomycin
Bleomycin is an effective antitumor drug. Its antitumor activity is believed to arise
from its ability to activate O2 and to cleave DNA oxidatively in a double strand fashion.
The active intermediate is a low-spin FeIII–OOH species.
Que, L., Jr., in Bioinorganic Catalysis, Reedijk, J. Ed; First Edition,
Marcel Dekker; Inc, New York, 1993; p 347
CATECHOL OXIDASE
Active site structure
Generally accepted mechanism of
Catechol oxidase
B.Krebs et al Nat.Struct.Biol. 5 (1998) 1084
B.Krebs et al J.Biol.Inorg.Chem. 4 (1999) 56
J.Reedijk et al Chem.Soc.Rev. 35 (2006) 814
TYROSINASE
diphenolase
cycle
3H+
O
O
O
2+
N Cu
Cu2+ N
N
N
O
2H+
oxy-D
+ H2O
O
HO
O
N Cu2+
Cu2+ N
N
N
O
H
met
HO
N Cu2+ O Cu2+
N
O
oxy
H+
O
N Cu2+ O Cu2+ N
N
N
O
oxy-T
OH
monophenolase
cycle
OH
O2
+
2H
+ H2O
+
H
O
O
O
2+
N Cu
Cu2+ N
N
N
O
met-D
O
OH
O
N Cu+ Cu+ N
N
N
deoxy
TYROSINASE MIMICS
Manganese, Iron and Copper in
Biomimetic Oxidation Catalysis
MANGANESE, IRON AND COPPER IN BIOMIMETIC
OXIDATION CATALYSIS
OXIDANTS
Molecular oxygen Ο2
Hydrogen peroxideΗ2Ο2
Η2 Ο 2
1.
Mild oxidant
2.
Cheap
3.
Easily available
4.
Environmental friendly (Η2Ο the only side
product)
5.High content of active oxygen (47%)
Mechanisms of Metal-catalyzed Oxidations: General Considerations
Metal–oxygen species
Heterolytic oxygen transfer
early transition metals (Mo, W, Re, V, Ti, Zr)
later transition metals (Ru,Os)
and particularly first row elements (Cr, Mn, Fe)
Peroxometal versus oxometal pathways
MΝ(SALEN) CATALYSTS
The epoxidation reaction:
Structure of a typical Mn(salen) complex
Jacobsen’s Mn(salen) catalysts
Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N., J. Am. Chem. Soc. 1990, 112, 2801-2803
Zhang, W.; Jacobsen, E. N., J. Org. Chem. 1991, 56, 2296-2298
Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L., J. Am. Chem. Soc. 1991, 113, 7063-7064
Berkessel’s imidazole tethered Mn(salen) complex
Berkessel, A.; Frauenkron, M.; Schwenkreis, T.; Steinmetz, A., J. Mol. Catal. A-Chem. 1997, 117, 339-346
Jacobsen’s PyO tethered Mn(salen) complex
Finney, N. S.; Pospisil, P. J.; Chang, S.; Palucki, M.; Konsler, R. G.; Hansen, K. B.; Jacobsen, E. N., Angew. Chem.-Int. Edit. Engl. 1997, 36, 1720-1723
Katsuki’s conformationally fixed Mn(salen) complex
Ito, Y. N.; Katsuki, T., Tetrahedron Lett. 1998, 39, 4325-4328
Mn-porphyrins
[Mn(Cl8tdcpp)]+, a “third generation” porphyrin complex
Meunier, B., Chem. Rev. 1992, 92, 1411-1456
Manganese-Me3tacn Complexes and Derivatives
Schematic structure of dinuclear manganese complexes that can be formed with the ligand Me3tacn ligand
under different synthetic conditions
de Boer, J. W.; Brinksma, J.; Browne, W. R.; Meetsma, A.; Alsters, P. L.; Hage, R.; Feringa, B. L., J.Am. Chem. Soc. 2005, 127, 7990-7991
Other Mn Complexes
Schematic drawing of the ligands tptn and R,R-mcp
Brinksma, J.; Hage, R.; Kerschner, J.; Feringa, B. L., Chem. Commun. 2000, 537-538
Murphy, A.; Dubois, G.; Stack, T. D. P., J. Am. Chem. Soc. 2003, 125, 5250-5251
Formation of the peroxycarbonate complex (A) by the direct reaction of
peroxymonocarbonate and (B) by the reaction of a peroxy complex with hydrogencarbonate
Lane, B. S.; Vogt, M.; DeRose, V. J.; Burgess, K., J. Am. Chem. Soc. 2002, 124, 11946-11954
Manganese Catalysts Containing Phenol-oxazoline Ligands
Hoogenraad, M.; Kooijman, H.; Spek, A. L.; Bouwman, E.; Haasnoot, J. G.; Reedijk, J., Eur. J. Inorg.Chem. 2002, 2897-2903
Manganese Catalysts Containing Acetylacetone-based Schiff Base Ligands
F 3C
CF3
N
N
H
N
O
O
F 3C
CF3
H3C
CH3
N
N
N
O
N
O
H3C
CH3
OH
Ag. Stamatis, P. Doutsi, Ch. Vartzouma, K.C. Christoforidis, Y. Deligiannakis, M. Louloudi, J. Mol. Catal. A 297 (2009), 44
Ch. Vartzouma, E. Evaggellou, Y. Sanakis, N. Hadjiliadis, M. Louloudi, J. Mol. Catal. A 263 (2007), 77
M. Louloudi, K. Mitopoulou, E. Evaggelou, Y. Deligiannakis, N. Hadjiliadis, J. Mol. Catal. A 198 (2003), 231
IRON COMPLEXES
Kim, C.; Dong, Y. H.; Que, L., J. Am. Chem. Soc. 1997, 119, 3635-3636
Chen, K.; Costas, M.; Kim, J. H.; Tipton, A. K.; Que, L., J. Am. Chem. Soc. 2002, 124, 3026-3035
Ryu, J. Y.; Kim, J.; Costas, M.; Chen, K.; Nam, W.; Que, L., Chem. Commun. 2002, 1288-1289
Wada, A.; Ogo, S.; Nagatomo, S.; Kitagawa, T.; Watanabe, Y.; Jitsukawa, K.; Masuda, H., Inorg. Chem. 2002, 41, 616-618
Roelfes, G.; Lubben, M.; Leppard, S. W.; Schudde, E. P.; Hermant, R. M.; Hage, R.; Wilkinson, E. C.;Que, L.; Feringa, B. L., J.
Mol.Catal. A-Chem. 1997, 117, 223-227.
Roelfes, G.; Lubben, M.; Hage, R.; Que, L.; Feringa, B. L., Chem. Eur. J. 2000, 6, 2152-2159
COPPER COMPLEXES
Oxidation of 3,5-di-t-butylcatechol (DTBC) to 3,5-di-t-butylquinone (DTBQ) with Ο2
(DTBC) oxidation to (DTBQ)
with 71% yield
D.Zois, Ch. Vartzouma, Y. Deligiannakis, N. Hadjiliadis, L. Casella, E. Monzani, M. Louloudi, J. Mol. Catal. A 261 (2007), 306-317
E. Monzani, L. Quinti, A. Perotti, L. Casella, M. Gullotti, L. Randaccio,S. Geremia, G. Nardin, P. Faleschini, G. Tabbi, Inorg. Chem. 37
(1998) 553–562
M. Gullotti, L. Santagostini, R. Pagliarin, A. Granata, L. Casella, J. Mol.Catal.: A Chem. 235 (2005) 271–284
Catalytic cycle for the oxidation of DTBC by the dinuclear copper(II) complexes with O2
(DTBC) to (DTBQ) with
62% yield
M. Louloudi, K. Mitopoulou, E. Evaggelou, Y. Deligiannakis, N. Hadjiliadis, J. Mol. Catal. A 198 (2003) 231–240
HETEROGENEOUS vs HOMOGENEOUSCATALYSIS
ADVANTAGES:
*
*
*
*
DISADVANTAGES:
*
*
*
Easy recovery of the catalyst
Catalyst protection by the support
Other benefits from the support:
reactivity & selectivity
No metal leaching --- environmental
friendly procedure
Catalyst reuse
Reduced reactivity of the active catalyst centres
H2O2 dismutation by the support
Examples of Different Inorganic Supports
ΤΑCN complex on silica surface
Catalyst immobilized into zeolite
“Salen” catalyst into MCM-41
“Salen” catalyst into clay layers
biomimetic ligand
HETEROGENEOUS
CATALYSTS
carbon chain
labile ligands
M
support
metal ion
Schematic representation of supported metal complexes : heterogeneous catalysts
HYBDID ORGANIC-INORGANIC MATERIALS
silica gel
L: ligand
biomimetic ligand
carbon chain
O
labile ligands
Si
O
M
L
Si
SiO2
O
Si
OH
O
support
metal ion
O
Si
O
SiO2
Synthetic strategy
Si
L
M
The Active Catalyst
O
Si
O
OH
Biomimetic complex
Supported homogeneous catalysts
O
Si
O
SiO2
Si
L
M
O
Si
The same coordination environment & immobilization
by covalent bond
OH
O
L'MLn-1
MLn
encapsulation
MLn
...
MLn
Immobilization on a membrane
Rj + Pj / διαλύτης 2
MLn* / διαλύτης 1
L'=L
Silica modification via sol-gel procedure
The same coordination environment & immobilization by covalent bond
MLn
L'MLn-1
L'=L
Possible evolution of a simple Q-type center during sol-gel reaction:
15 different species can be detected
Hydrolysis and condensation reactions are pH-dependant.
Development and condensation of silicon-centeres during the gel
formation are also pH-dependent
HYBDID ORGANIC-INORGANIC MATERIALS
silica gel
L: ligand
O
Si
Synthetic strategy
O
L
Si
SiO2
O
Si
OH
O
O
Si
O
SiO2
Si
L
M
The Active Catalyst
O
Si
O
OH
Biomimetic complex
Synthetic procedures of supported metal complexes used as heterogeneous catalysts
Preparation of an organically modified mesoporous silica
via sol-gel methodology
Synthesis of silicon-precursors
1.Hydrosililation
2.
Nucleophilic abstraction of halogens
Synthesis of silicon-precursors
3. Grignard-reactions
4. Condensation reactions
Synthetic procedures of supported metal complexes used as heterogeneous catalysts
MANGANESE, IRON AND COPPER IN
HETEROGENEOUS BIOMIMETIC OXIDATION
CATALYSIS
OXIDANTS
Molecular oxygen Ο2
Hydrogen peroxideΗ2Ο2
HETEROGENEOUS vs HOMOGENEOUSCATALYSIS
ADVANTAGES:
*
*
*
*
DISADVANTAGES:
*
*
*
Easy recovery of the catalyst
Catalyst protection by the support
Other benefits from the support:
reactivity & selectivity
No metal leaching --- environmental
friendly procedure
Catalyst reuse
Reduced reactivity of the active catalyst centres
H2O2 dismutation by the support
Heterogeneous biomimetic oxidation catalysts
Manganese-Me3tacn Catalysts
D.E.De Vos, S.Wildeman, B.F.Sels, P.J.Grobet, P.A.Jacobs, Angew. Chem. Int. Ed. Engl., 38, 1999, 980
Mn(salen) catalysts
A.R.Silva, K.Wilson, J.H.Clark, C.Freire, Micr. Mesop. Mater., 2006, 128
Mn-Heterogeneous catalysts with Acetylacetone-based Schiff Bases
CH3
N
R
N
O
O
R
O
N
O
Si O
OH
N
CH3
R=CH3 ,
R=CF3 ,
G-A
G-B
Ch.Vartzouma, El.Evaggellou, Y.Sanakis, N.Hadjiliadis, M. Louloudi. Journal of Molecular Catalysis A: Chemical 263, 2007, 77
Ag.Stamatis, D.Giasafaki, M. Louloudi. Journal of Molecular Catalysis A: Chemical 2009, in press
Mn-porphyrins
K.J.Ciuffi, H.C.Sacco, J.C.Biazzotto, E.A.Vidoto, O.R.Nascimento, O.A.Serra, Y.Iamamoto, J.Non-Cryst. Solids, 273, 2000, 100
E.R. Milaeva, O.A.lGerasimova, A.L. Maximov, E.A. Ivanova, E.A. Karachanov, N. Hadjiliadis, M. Louloudi,
Catalysis Communications 8 (2007), 2069
Mn-Heterogeneous catalysts with Imidazole-based biomimetic ligands
A.Serafimidou, Ag.Stamatis, M.Louloudi. Cat. Comm. 9,2008, 35
D.Zois, Ch.Vartzouma, Y.Deligiannakis, N.Hadjiliadis,L.Casella, E. Monzani, M.Louloudi.
Journal of Molecular Catalysis A: Chemical 261, 2007, 306
Heterogeneous Copper catalysts
Oxidation of 3,5-di-t-butylcatechol (DTBC) to 3,5-di-t-butylquinone (DTBQ) with Ο2
O
OH
OH
C-(CH3)3
C-(CH3)3
O
O2
καταλύτης
C-(CH3)3
DTBC
C-(CH3)3
DTBQ
M. Louloudi, K. Mitopoulou, E. Evaggelou, Y. Deligiannakis, N. Hadjiliadis, J. Mol. Catal. A 198 (2003), 231
D.Zois, Ch. Vartzouma, Y. Deligiannakis, N. Hadjiliadis, L. Casella, E. Monzani, M. Louloudi, J. Mol. Catal. A 261 (2007),
Oxidation of 3,5-di-t-butylcatechol (DTBC) to 3,5-di-t-butylquinone (DTBQ) with Ο2
Table 2.
catalyst
Cu2(LA)
Cu2(LA).SiO2
Cu(LB)
Cu(LB).SiO2
DTBQ formation (%)
(TON)a
24h
48h
60.0
70.6
(400)
(471)
69.0
92.6
(460)
(617)
23.0
37.1
(153)
(247)
49.7
78.1
(331)
(521)
DTBC conversion (%)
(TON)b
24h
48h
68.6
79.0
(457)
(527)
90.0
96.0
(600)
(640)
24.5
38.2
(163)
(255)
61.4
88.7
(409)
(591)
a
DTBQ2LA
DTBQ2LA.SiO2
DTBQB
100
DTBQB.SiO2
90
TON : moles of DTBQ formed per mole of catalyst
b
TON : moles of DTBC converted per mole of catalyst
80
% oxidation
70
60
50
40
30
20
10
0
DTBQ formation
DTBC conversion
Conditions: [3,5-di-t-butylcatechol]:[catalyst]:[base] = 200:0.3:3 ή 200:0.3:30
Heterogeneous Iron catalysts
Tetrahedron 2006,62,9911-9918
Heterogeneous Iron catalysts
CF3
F3C
O
N
OH
N
O
F3C
O
OH
O
Si
O
N
CF3
L2SiO2
FeL2Cl2
FeL2-( SiO3/2)n.zSiO2
90
80
160
70
120
Total yield %
Total yield (%)
200
κυκλοεξενόνη
κυκλοεξενόλη
Εποξείδιο
100
80
60
50
40
30
40
20
0
0
20
40
60
H2O2 μmol
80
100
10
0
1st-use
2nd-use
G.Bilis, M.Louloudi et al. 2009, unpublished results
3rd-use
4th-use
Heterogeneous Iron catalysts
N
O
HO
HO
O Si
O
N
O
N
O
cyclohexenone
L1SiO2
FeL1Cl
80
70
200
total yield (%) %
Total yield (%)
90
2
[FeL1-SiΟ3/2]m.zSiΟ2
240
cyclohexenol
epoxide
160
120
80
60
50
40
30
20
40
10
0
0
0
20
40
60
80
100
120
1st-use
2nd-use
3rd-use
H2O2 (μmol)
G.Bilis, M.Louloudi et al. 2009, unpublished results
4th-use
5th-use
Advanced Catalysis: Biomimetic Oxidation Catalysis
Oxidation
Catalysis
Biomimetics
Heterogeneous
Catalysts
‘Green Chemistry’
CATALYSIS
HETEROGENEOUS CATALYSTS
Ο2 AND Η2Ο2 AS OXIDANTS
Current Processes

New Processes
stoichiometric
high temperature
catalytic
low temperature
homogeneous catalysts
supported catalysts
pollutant oxidants
clean oxidants
(Cr, Mn, Co salts, ClO-, peracids) (O2, H2O2)
Remove
pollutants
phenols
energy saving
environmental friendly
oxidants
New for selective oxidation of hydrocarbons
oxidations
to be found fine chemical applications
University of Ioannina,
GREECE
Thank you for your attention