C -0.5723379 1.1416733 5.8974023

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S1
The SUPERBULKY Pn LIGAND COMPLEXES [CpBIGFe(η5-P5)] and
[(CpBIGFe)2(η4:4P4)] – SYNTHESIS AND CHARACTERIZATION
Sebsatian Heinl, Gabor Balazs and Manfred Scheer*
Institut für Anorganische Chemie, Universitätsstraße 31, 93053 Regensburg,
Email: [email protected]
1. Crystallographic details
The crystal structure analyses were performed either on an Oxford Diffraction Gemini R Ultra
CCD diffractometer (1b, 4) or an Oxford Diffraction SuperNova diffractometer (3). For all
compounds an analytical absorption correction was carried out.[1] The structures were solved by
direct methods either of the program SIR-92[2] or SHELXS-97[3] and refined with least square
method on F2 employing SHELXL-97 with anisotropic displacements for non-H atoms.
Hydrogen atoms were located in idealized positions and refined isotropically according to the
riding model.
CCDC-982098 (1b), CCDC-982099 (3) and CCDC-982100 (4) contain the supplementary
crystallographic data for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: + 44-1223-336-033; e-mail:
[email protected]).
S2
Crystal data for 1b: C55H65FeP5, M = 936.77, space group P1;¯ (no.2), a = 13.8286(11) Å,
b = 13.8982(8) Å, c = 14.6573(8) Å, α = 96.579(4)°, β = 106.372(6)°, γ = 103.405(6)°, V =
2579.9(3) Å3, Z = 2, μ = 4.061 mm-1, F(000) = 992.0, T = 123 K, 24959 reflections measured,
9182 unique (Rint = 0.0365), R1 = 0.0578, wR2 = 0.1457 for I > 2σ(I); CCDC-982098.
Figure S 1: Molecular structure of 1b in the crystal. H atoms and disorder are omitted for
clarity; thermal ellipsoids drawn at 50% probability level. Selected bond lengths [Å] and angles
[°]: P1-P2 2.105(1), P2-P3 2.107(1), P3-P4 2.108(1), P4-P5 2.106(1), P1-P5 2.109(1), FeP5,centroid 1.5537(5), Fe-Cpcentroid 1.7281(5), Fe-P5,centroid- Fe-Cpcentroid 179.44(3).
S3
Crystal data for 3 · 2 C7H8: C128H146Fe2O4, M = 1860.15, space group P21/c (no.14), a =
11.6361(3) Å, b = 24.0846(5) Å, c = 18.4036(4) Å, β = 99.730(2)°, V = 5083.4(2) Å3, Z = 2, μ =
2.708 mm-1, F(000) = 1996.0, T = 123 K, 80290 reflections measured, 10561 unique (Rint =
0.0334), R1 = 0.0373, wR2 = 0.0935 for I > 2σ(I); CCDC-982099.
Figure S 2: Molecular structure of 3 in the crystal. H atoms, solvent molecules and disorder are
omitted for clarity; thermal ellipsoids drawn at 50% probability level. Selected bond lengths [Å]
and angles [°]: Fe1-Fe1’ 2.6180(3), Fe1-C1 1.756(2), Fe1-C2 1.950(2), Fe1-C2’ 1.950(2), FeCpcentroid 1.8055(2), C1-Fe1-Fe1’ 94,38(5), Fe1-C2-Fe1’ 84.60(5), C2-Fe1-C2’ 95,40(6).
S4
Table S 1 Fe-Fe bond lengths of selected of trans-[CpRFe(CO)2]2 complexes.
CpR
Fe-Fe bond length [Å]
CpBIG, C5(4-nBuC6H4)5, (3)
2.6180(3)
Cp, C5H5
2.534(2)4
Cp*, C5Me5
2.560(1)5
Cp’, C5H4tBu
2.550(1)6
CpiPr, C5iPr5
2.600(2)7
CpBn, C5(CH2Ph)5
2.5718(1)8
The Cambridge Crystallographic Data Centre was searched through for trans-[CpRFe(CO)2]2
complexes and no longer Fe-Fe bond length than in case of 3 was found.
S5
Crystal data for 4 · 0.5 CH2Cl2 · CH3CN: C112.5H134ClFe2NP4, M = 1771.25, space group P1;¯
(no.2), a = 16.3602(5) Å, b = 16.8056(5) Å, c = 21.5861(5) Å, α = 73.085(2)°, β = 71.808(2)°, γ
= 61.207(3)°, V = 4870.3(3) Å3, Z = 2, μ = 3.619 mm-1, F(000) = 1890.0, T = 124 K, 35298
reflections measured, 18851 unique (Rint = 0.0253), R1 = 0.0797, wR2 = 0.1711 for I > 2σ(I);
CCDC-982100.
Figure S 3 Molecular structure of 4 in the crystal. H atoms, solvent molecules and disorder are
omitted for clarity; thermal ellipsoids drawn at 50% probability level. Selected bond lengths [Å]:
P1-P2 2.100(2), P2-P3 2.3684(2), P3-P4 2.098(2), P1∙∙∙P4 3.560(2), Fe1-Fe2 2.6307(6). Selected
angle [°]: CpPlane-CpPlane 22.0(2).
S6
Table S 2 Comparison of selected bond lengths [Å] of [(CpRFe)2(µ,η4:4-P4)] complexes.
CpR
Fe1-Fe2
P1-P2
P2-P3
P3-P4
P1∙∙∙P4
2.6307(6)
2.100(2)
2.3684(2)
2.098(2)
3.560(2)
Cp’’, C5H3tBu2[9]
2.616(1)
2.081(2)
2.385(2)
2.094(2)
3.57
Cp’’’, C5H2tBu3[10]
2.6430(8)
2.0877(13)
2.368(2)
2.0877(13)
3.55
2.603(1)
2.090(2)
2.436(2)
2.093(2)
3.550(2)
4: CpBIG,
C5(4-nBuC6H4)5
Cp2Si,
C5H3(SiMe3)2[11]
S7
2. Computational details
All calculations have been performed with the TURBOMOLE program package.[ 12 ] The
geometries have been optimized without any symmetry restrains at the RI-[13]B3LYP[14]/def2TZVP[15] level of theory including the Multipole Accelerated Resolution of Identity (MARI-J)
approximation[ 16 ]. To obtain the orbital energies single point calculations without the RI
approximation have been performed.
Table S 4. Calculated orbital energies and HOMO-LUMO gap for [CpRFe(η5-P5)] at the
B3LYP/def2-TZVP level of theory.
HOMO-LUMO (eV)
4.304
HOMO (eV)
LUMO (eV)
-6.339
-2.035
C5H4Ph
4.141
-6.264
-2.123
C5H3Ph2
4.043
-6.196
-2.153
C5H2Ph3
4.017
-6.166
-2.149
C5HPh4
4.072
-6.187
-2.115
C5Ph5
4.071
-6.164
-2.093
C5H4(CF3)
4.182
-6.563
-2.382
C5H3(CF3)2
4.063
-6.761
-2.699
C5H2(CF3)3
3.965
-6.938
-2.973
C5H(CF3)4
3.881
-7.079
-3.199
C5(CF3)5
3.795
-7.211
-3.426
C5(CH3)5
4.414
-6.149
-1.735
CpR
C5H5
S8
Figure S 4: Calculated orbital energies (eV) for [CpRFe(η5-P5)] at the B3LYP/def2-TZVP level
of theory.
S9
Figure S 5: Calculated orbital energies (eV) for [CpRFe(η5-P5)] at the B3LYP/def2-TZVP level
of theory.
S 10
Figure S 6: Isosurfaces of the HOMO and LUMO orbitals in [{C5(C6H5)5}Fe(η5-P5)] calculated
at the B3LYP/def2-TZVP level of theory.
S 11
Figure S 6: Isosurfaces of the HOMO and LUMO orbitals in [{C5(CF3)5}Fe(η5-P5)] calculated at
the B3LYP/def2-TZVP level of theory.
S 12
Table S 5. Cartesian coordinates of the optimized geometry of [{C5(C6H5)5}Fe(η5-P5)] at the
B3LYP/def2-TZVP level of theory.
Atom
Fe
P
P
P
P
P
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
H
C
H
C
H
C
H
C
H
C
H
C
H
C
H
C
H
C
H
x
0.7502552
3.1084942
2.5815462
0.9042203
0.3950688
1.7568419
-0.5972412
-1.2986193
-0.6637486
0.4302042
0.4713604
-1.0353828
-2.5821782
-1.1841911
1.2290059
1.3215484
-2.3619661
-0.1575739
-2.7655593
-3.6824554
-1.4300027
-1.5178188
1.2875490
1.8628300
0.7098490
2.7074777
-2.7969952
-3.0591574
-0.5935075
0.8759651
-4.0006436
-1.9387273
-4.9192013
-3.5728700
-1.9796724
-1.1951906
-2.0628784
-1.3562556
1.9651379
0.7937093
2.5443872
1.8189391
1.4597548
-0.3627713
3.4577584
3.2039984
y
1.0551418
1.6195685
0.4513704
1.3567473
3.0849382
3.2469258
-0.6217800
0.5691337
1.0888695
0.2196799
-0.8377846
-1.5801922
1.0469888
2.1944431
0.2804425
-2.0536644
-2.0284652
-2.1210312
1.2489016
1.2281619
1.9544313
3.4490376
-0.8494333
1.4478146
-3.3131733
-1.9958255
-2.9763673
-1.6379666
-3.0652710
-1.8066617
1.6337292
1.0994079
1.6085562
1.0645819
2.9385634
0.9877362
4.4345019
3.6563429
-0.8153426
-1.7619501
1.4805626
2.3402195
-4.4738880
-3.3868116
-3.1562564
-1.0368897
z
.
4.3306602
4.5335959
2.8463175
1.9211674
3.0362151
4.6512092
4.3787849
4.7724189
5.9519626
6.2873614
5.3151920
3.3312127
4.1960318
6.7974952
7.5388277
5.3971129
3.3320675
2.3872806
2.8250654
5.0429753
8.1549528
6.2791113
8.3639214
7.9742922
5.3836383
5.5699359
2.4142378
4.0607766
1.4668249
2.3745841
2.3197386
2.1458898
4.5370562
6.1063859
8.9670664
8.5791943
7.0919121
5.2311513
9.5763144
8.0588117
9.1839158
7.3668555
5.5272621
5.2663910
5.7087636
5.6026001
S 13
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
H
H
H
H
H
-1.9152985
-3.8279033
0.1051377
-5.0828911
-4.1151003
-5.7548212
-2.2943034
-2.1611153
-2.3073226
2.6011616
1.9945308
3.0319376
2.8386857
0.9625648
4.5308038
-6.0450935
-2.7181479
3.1337242
3.4250600
-2.2541930
-3.4960984
-3.3074215
-3.4648841
1.8178772
1.7894056
1.7411982
4.1856343
2.7274646
5.4002132
0.3492562
-1.7024722
2.3958043
-4.4008662
-5.4359109
-3.0847592
2.1191614
4.9553619
0.3759067
-5.3049542
-4.2316061
1.4737707
2.4364936
0.7423028
3.1727200
1.2541850
5.2130785
8.4399769
10.0136633
6.6671909
9.9899394
10.1968070
9.4959290
5.6858305
5.5146245
5.8360291
2.7776110
9.0729009
10.9324887
5.7931778
0.7548199
S 14
Table S 6. Cartesian coordinates of the optimized geometry of [{C5(CF3)5}Fe(η5-P5)] at the
B3LYP/def2-TZVP level of theory.
Atom
Fe
P
P
P
P
P
C
C
C
C
C
C
F
F
F
C
F
F
F
C
F
F
F
C
F
F
F
C
F
F
F
x
0.7893969
3.1554205
2.5910756
0.8803867
0.3877711
1.7935987
-0.5245223
-1.2178088
-0.5723379
0.5348413
0.5802701
-1.1225389
-1.1549181
-2.3785475
-0.4160340
-0.9974161
-0.1635993
-1.1217809
-2.2004644
1.5469219
2.8286582
1.2558457
1.4615887
-2.5086695
-2.8069606
-2.4490164
-3.5354677
1.3645104
1.9619196
0.5578976
2.3212331
y
1.1277194
1.7119934
0.5636267
1.4715378
3.1814262
3.3281540
-0.5591116
0.6260425
1.1416733
0.2864236
-0.7499572
2.2793331
3.4577780
1.9694895
2.4646258
-1.5904731
-1.7317495
-2.7844235
-1.2969577
-1.9338219
-1.5647636
-2.7628935
-2.6406004
1.1540182
2.3880538
1.2053556
0.3579949
0.3586009
1.5450217
0.1347988
-0.5700298
z
.
4.2638311
4.4086392
2.7148207
1.8487935
3.0037557
4.5875622
4.3226942
4.7259280
5.8974023
6.2045090
5.2152080
6.7603807
6.1265741
7.1361569
7.8771056
3.2950737
2.2586360
3.9064604
2.7957117
5.2010837
5.3157917
6.2198970
4.0700249
4.1040051
4.5188321
2.7664927
4.4519575
7.4860297
7.6539030
8.5411511
7.5344170
S 15
Figure S 7: IR spectrum of [CpBIGFe(CO)2]2 (1b) in toluene. νCO [cm-1] are assigned. For
comparison see also reference [17].
Figure S 8: Section of the IR spectrum of [CpBIGFe(CO)2]2 (1b) in toluene. νCO [cm-1] are
assigned.
S 16
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