S1
Synthesis and Characterization of the Novel 1,2,4-Triphosphaferrocene
[Cp*Fe(η5-P3C2Mes2)] containing Sterically Demanding Mesityl Groups
Claudia Heindl†, Andrea Schindler†, Michael Bodensteiner†, Eugenia V. Peresypkina‡,§,
Alexander V. Virovets‡,§ and Manfred Scheer†*
†
Institut für Anorganische Chemie, Universität Regensburg, Universitätsstraße 31, 93040
Regensburg
‡
Nikolaev Institute of Inorganic Chemistry SB RAS, Ak. Lavrentiev prosp. 3, Novosibirsk
630090, Russia
§
Novosibirsk State University, ul. Pirogova 2, Novosibirsk 630090, Russia
E-mail: Manfred.Scheer@ur.de
Supplemental Materials
Figure S 1: 31P{1H} NMR spectrum (CD2Cl2, 121.49 MHz, 293 K) of 1.
S2
Figure S 2: 31P{1H} NMR spectrum (CD2Cl2, 242.98 MHz, 293 K) of 1.
Crystallographic data
The crystal of 1 appeared to be a racemic twin. The refinement of twinning model results in
0.71/0.29 ratio of the components. Probably due to the intermediate size of domains and
consequent partial interference between their diffraction beams, the resulting diffraction intensities
fail to be described by twinning solely. The residual electron density contains peaks up to 4.3 e·A3
corresponding to the whole structure reflected by the mirror plane perpendicular to the a axis that
do not belong to the chiral P212121 space group. At the same time, this mx plane is
crystallographically equivalent to the racemic twin operator in the mmm Laue class. Therefore, the
twinning manifests itself also as a disorder of the whole structure in the ratio refined to 0.89/0.11.
After introduction of the disorder the residual electron density peaks did not exceed 0.48 e·A-3. All
S3
non-hydrogen atoms of major component were refined anisotropically. The heavy atoms, Fe and
P, of the minor part were refined freely in anisotropic approximation. The light atoms of the minor
part were treated isotropically with a number of geometric constraints. The distances P-C of the
cyclo-P3C2 were restrained to be similar (SADI instruction in SHELX). The phenyl groups of
mesityl were approximated as perfect hexagons (AFIX 66 in SHELX) and refined with identical
displacement parameters within each group. The Cp* were refined as a ‘variable metric’ rigid
group (AFIX 9 in SHELX) with identical displacement parameters for C atoms of the Cp ring. All
cyclic fragments were forced to be planar. The positions of the hydrogen atoms were not included
into the refinement. The resulting quality factors improved from R1= 0.0868, wR2= 0.1913 and S
= 2.356 to R1= 0.0344, wR2= 0.0799 and S = 0.979.
Crystallographic data and details of the diffraction experiments are given in Table 1. CIF files with
comprehensive information on the details of the diffraction experiments and full tables of bond
lengths and angles for 1 and 1·CH2Cl2 are deposited in Cambridge Crystallographic Data Centre
under the deposition codes CCDC-1018495 and CCDC-1018496, respectively.
S4
Figure S 3: The model of the disorder (component ratio 0.89/0.11) in racemically twinned (ratio 0.71/0.29) structure
of 1. The minor position is shown by the dashed lines.
S5
Table S 1. Experimental details for 1 and 1·CH2Cl2
1
1·CH2Cl2
Chemical formula
C30H37FeP3
C30H37FeP3·CH2Cl2
Mr
542.59
631.28
Crystal system, space group
Orthorhombic, P212121
Monoclinic, P21/n
Temperature (K)
123
123
a, b, c (Å)
9.0115 (1), 17.0449 (3), 17.5260 (4)
13.6048 (5), 9.0063 (3), 25.3402 (9)
 (°)
90
102.784 (4)
V (Å3)
2692.00 (8)
3027.94 (18)
Z
4
4
F(000)
1137
1320
Dx (Mg m-3)
1.339
1.385
Radiation type
Cu K
Mo K
 (mm-1)
6.29
0.85
Crystal shape, colour
Red block
Dark red plate
Crystal size (mm)
0.13 × 0.10 × 0.02
0.27 × 0.14 × 0.05
Diffractometer
Xcalibur, Ruby, Gemini ultra
diffractometer
SuperNova, Single source at offset,
Eos diffractometer
Absorption correction*
Analytical
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.5 (release 08-05-2007
CrysAlis171 .NET) (compiled May 8
2007, 13:10:02).
Analytical
CrysAlis PRO, Agilent Technologies,
Version 1.171.36.28 (release 01-022013 CrysAlis171 .NET) (compiled
Feb 1 2013, 16:14:44).
Tmin, Tmax
0.594, 0.881
0.832, 0.959
No. of measured, independent
and observed [ > 2(I)]
reflections
6840, 3604, 3133
12309, 6799, 4078
Rint
0.033
0.038
max (°)
58.9
29.2
(sin /)max (Å-1)
0.555
0.686
Range of h, k, l
h = -109, k = -1718, l = -1915
h = -1815, k = -711, l = -3217
R[F2 > 2(F2)], wR(F2), S
0.034, 0.080, 0.98
0.044, 0.089, 0.86
No. of reflections, parameters,
restraints
3604, 408, 24
6799, 345, 0
H-atom treatment
H-atom parameters constrained
H-atom parameters constrained
max, min (e Å-3)
0.48, -0.29
0.49, -0.57
Crystal data
Data collection
Refinement
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Absolute structure parameter
0.292 (7)
-
* Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C.
Clark & J.S. Reid. [Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897]
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Molecular structure of 1.
Figure S 4: The molecular structure of 1·CH2Cl2 (ellipsoids of 50% probability) and numerating scheme of 1·CH2Cl2
being identical to 1.
S8
Table S 2. Selected geometric parameters (Å, º) for 1 and 1·CH2Cl2
Bond lengths
1*
1·CH2Cl2
Bond lengths
1
1·CH2Cl2
Fe1—P1
2.3095 (17)
2.2958 (8)
C13—C20
1.508 (8)
1.515 (4)
Fe1—P2
2.3017 (16)
2.2969 (8)
C14—C15
1.389 (8)
1.381 (4)
Fe1—P3
2.3601 (10)
2.3623 (8)
C15—C16
1.386 (8)
1.379 (4)
Fe1—C1
2.212 (5)
2.207 (3)
C15—C19
1.491 (7)
1.518 (4)
Fe1—C2
2.216 (5)
2.217 (3)
C16—C17
1.395 (9)
1.401 (4)
Fe1—C21
2.106 (5)
2.104 (3)
C17—C18
1.521 (8)
1.494 (4)
Fe1—C22
2.087 (5)
2.087 (2)
C21—C30
1.506 (9)
1.498 (4)
Fe1—C23
2.079 (5)
2.088 (3)
C21—C25
1.426 (9)
1.431 (4)
Fe1—C24
2.120 (5)
2.099 (3)
C21—C22
1.412 (7)
1.430 (4)
Fe1—C25
2.138 (4)
2.122 (3)
C22—C23
1.414 (7)
1.426 (4)
P1—C2
1.780 (5)
1.777 (3)
C22—C29
1.504 (7)
1.498 (4)
P2—C1
1.790 (5)
1.774 (3)
C23—C24
1.447 (7)
1.419 (4)
P3—C2
1.768 (5)
1.761 (3)
C23—C28
1.508 (7)
1.494 (4)
P3—C1
1.767 (5)
1.759 (3)
C24—C27
1.500 (7)
1.514 (4)
P1—P2
2.123 (2)
2.1180 (11)
C24—C25
1.434 (8)
1.427 (4)
C1—C12
1.496 (7)
1.517 (4)
C25—C26
1.495 (5)
1.497 (4)
C2—C3
1.507 (7)
1.507 (4)
C1S—Cl1
-
1.775 (4)
C3—C4
1.421 (8)
1.407 (4)
C1S—Cl2
-
1.733 (3)
C3—C8
1.423 (8)
1.414 (4)
C4—C11
1.496 (8)
1.505 (4)
Bond lengths
1
1·CH2Cl2
C4—C5
1.379 (9)
1.390 (4)
P2—P1—C2
99.21 (18)
99.19 (10)
C5—C6
1.382 (9)
1.378 (4)
P1—P2—C1
99.60 (18)
98.86 (10)
C6—C7
1.387 (9)
1.383 (4)
C1—P3—C2
99.9 (2)
98.91 (13)
C6—C10
1.500 (7)
1.511 (4)
P2—C1—C12
117.3 (4)
117.7 (2)
C7—C8
1.380 (8)
1.390 (4)
P2—C1—P3
120.3 (3)
121.71 (15)
C8—C9
1.527 (8)
1.518 (4)
P3—C1—C12
122.4 (4)
120.50 (19)
C12—C17
1.405 (8)
1.409 (4)
P1—C2—P3
121.0 (3)
121.26 (16)
C12—C13
1.434 (8)
1.412 (4)
P1—C2—C3
116.8 (4)
117.57 (19)
P3—C2—C3
122.2 (4)
121.13 (19)
C13—C14
1.380 (7)
1.389 (4)
* the distances are listed only for major component.
S9
a
S 10
b
Figure S 5: The crystal packing (a) in 1 (for major component) and (b) in 1·CH2Cl2. The hydrogen atoms are not
shown.