In the format provided by the authors and unedited. SUPPLEMENTARY INFORMATION DOI: 10.1038/NCHEM.2840 Cooperative carbon-atom abstraction from alkenes in the core of a pentanuclear nickel cluster Contents: Manar M. Shoshani and Samuel A. Johnson* Department of Chemistry and Biochemistry, University of Windsor Sunset Avenue 401, Windsor, ON, N9B 3P4, (Canada) Fax: (+1) 519-973-7098 E-mail: sjohnson@uwindsor.ca 1: General 2 2: Experimental Synthesis and Characterization of (2) [Ni(P i Pr 3)] 5(µ-H) 4(µ 5-C) 2 NMR Scale Synthesis and Characterization of 2 and Organic Products 5 Synthesis and Characterization of (2*) [Ni(P i Pr 3)] 5(µ-H) 4(µ 5-13 C) 6 Synthesis and Characterization of (3) Ni 5(P i Pr 3) 3(µ 2-H) 3(CCPh)(H 2C=CHPh) 8 Reaction of 3 with P i Pr 3 + H 2 17 Synthesis and Characterization of (4) (Ni 5(P i Pr 3) 5(µ 2-H) 5(CC(Me)=CH 2). 19 Conversion of 4 to 2 23 Conversion of 1 to 2 in the Presence of added Functional Group Bearing Compounds 24 3: Crystallographic Information 26 NATURE CHEMISTRY www.nature.com/naturechemistry 1 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
General: Unless otherwise stated, all manipulations were performed under an inert atmosphere of nitrogen using either standard Schlenk techniques or an MBraun glove-box. Dry, oxygen-free solvents were employed throughout. Anhydrous pentane, toluene, and THF were purchased from Alfa Aesar and were argon packed and dried with either activated sodium or molecular sieves. Benzene-d6 and THF-d8 was dried by filtering through a plug of activated alumina. Isobutylene was purchased from Sigma-Aldrich and dried with activated molecular sieves. Styrene and ethylene, and carbon- 13-labelled ethylene were purchased from Sigma-Aldrich and their purity was confirmed through NMR spectroscopy. 1 H, 31 P{ 1 H} and 13 C{ 1 H} NMR spectra were recorded on a Bruker AMX Spectrometer operating at 300 MHz or 500 MHz with respect to proton nuclei. All chemical shifts are recorded in parts per million, and all coupling constants are reported in Hertz. 1 H NMR spectra were referenced to residual protons (C6D5H, δ 7.15; C7D7H, δ 2.09; C4D7HO, δ 1.73) with respect to tetramethylsilane at δ 0.00. 31 P{ 1 H} NMR spectra were referenced to external 85% H3PO4 at δ 0.00. 13 C{ 1 H} NMR spectra were referenced relative to solvent resonances (C6D6, δ 128.0; C7D8, δ 20.4; C4D8O, δ 25.37) Elemental analyses were performed at the Center for Catalysis and Materials Research, Windsor, Ontario. Experimental: Synthesis and Characterization of (2) [Ni(P i Pr3)]5(µ-H)4(µ5-C) A stirring solution of [( i Pr3P)Ni]5H6 (550 mg, 0.50 mmol) in 100 ml of n-pentane, was exposed to 2 equivalents of ethylene (0.0246 L, 1 mmol) through a Schlenk line. The solution was stirred for 0.25 hours. The dark brown solution was then evacuated and filtered through a plug of Celite and was concentrated until the precipitation of product was observed. The solution was left at 40 2
C for 40 hours, which afforded dark brown plates suitable for X-ray diffraction. A second crop also afforded crystals and a combined yield of 281 mg (46.5 %) was obtained. 1 H NMR (298 K, C6D6, 500 MHz): δ 7.17 (sextet, 2 JPH=2.45 Hz, 4 H, Ni-H), 1.40 (dd, 3 JHH= 7.1 Hz, 3 JPH= 12.4 Hz, 90 H, P(CH(CH3)2)3), 2.21 (septet of d/apparent octet, 3 JHH=7.2 Hz, 2 JPH= 7.6 Hz, 15 H, P(CH(CH3)2)3. 31 P{ 1 H} NMR (298 K, C6D6, 202.5 MHz): δ 52.4 (s, 5P, P(CH(CH3)2) 13 C{ 1 H} NMR (298 K, C6D6, 125.7 MHz): δ 20.7 (s, 30 C, P(CH(CH3)2)), 24.1 (d, 1 JPC=12.1 Hz, 15 C, P(CH(CH3)2) Anal Calcd. for C46H109Ni5P5: %C 49.74; %H 9.89. Found %C 49.96; %H 10.21. Figure 1: 1 H NMR of Cluster 2 in C6D6 3
Figure 2: 31 P{ 1 H} NMR of Cluster 2 in C6D6 4
Figure 3: 13 C{ 1 H} NMR of Cluster 2 in C6D6 NMR Scale Synthesis of 2 A solution of 1 (27 mg, 0.025 mmol) in 0.5 ml of benzene was transferred to a J-Young tube. Ethylene was introduced to the room temperature solution, until the sample was saturated. The reaction was left to stir for 15 min. 1 H NMR spectra was collected and showed the conversion of 1 to 2 as well as the growth of peaks corresponding to ethane and methane. 5
Figure 4: Crude 1 H NMR of synthesis of cluster 2 in C6H6 Synthesis and Characterization of (2*) [Ni(P i Pr3)]5(µ-H)4(µ5-13 C) A solution of [( i Pr3P)Ni]5H6 (28mg, 0.025 mmol) in 0.5 ml of n-pentane was transferred to a J- Young tube. The pressure of the J-young tube was then reduced using vacuum and 2 equivalents of carbon-13-labelled ethylene (1.22 ml,0.050 mmol) were introduced to the J-young tube and the reaction was left for 5 min. 1 H and 31 P{ 1 H}, 13 C{ 1 H} NMR spectra were collected and show the conversion to 1* 31 P{ 1 H} NMR (298 K, C7D8, 202.5 MHz): δ 50.5 (d, 2 JPC=20.5 Hz, 5P, P(CH(CH3)2) 13 C{ 1 H} NMR (298 K, C6D6, 125.7 MHz): δ 446.4 (sextet, 2 JPC=20.5 Hz, 1C, Ni- C); 6
Figure 5: Model of 13 C{ 1 H} NMR of Cluster 2* from coupling to 5 phosphines (red) and 13 C{ 1 H} NMR of Cluster 2* in d8-thf (blue) Figure 6: 13 C NMR of organic products in d8-thf 7
Synthesis and Characterization of (3) Ni5(P i Pr3)3(µ2-H)3(CCPh)(H2C=CHPh) A solution of an excess of styrene [C8H8 (756 mg, 7.27 mmol) in 10 ml of n-pentane was cooled to 40 C and added dropwise over the course of 0.25 h to a solution of [( i Pr3P)Ni]5H6 (800 mg, 0.727 mmol) in 5mL of n-pentane. The dark brown solution was stirred at 40 C for 0.5 h, then filtered through a plug of Celite and solvent was removed under vacuum until product precipitated. The solution was cooled to 40 C and after 16 h dark brown blocks suitable for X-ray diffraction were isolated by filtration. A second crop also afforded crystals and a combined yield of 376 mg (52.7 %) was obtained. Isomer A 1 H NMR (298 K, C6D6, 500 MHz): δ 21.12 (dd, 2 JPH=30.2 Hz, 2 JPH=10.3 Hz 1H, Ni-H), 15.77 (tm, 2 JPH=15.4 Hz, 1H, Ni-H), 13.90 (d, 2 JPH=22.4 Hz, 1H, Ni- H), 0.79-1.02 (4x dd, 3 JHH= 7.2 Hz, 3 JPH= 13.6 Hz, 36 H, P(CH(CH3)2)3), 1.42 (dd, 3 JHH= 7.1 Hz, 3 JPH= 12.7 Hz, 18 H, (CH(CH3)2)3), 1.42 (septet of d/apparent octet, 3 JHH=7.1 Hz, 2 JPH= 14.5 Hz, 3H, P(CH(CH3)2), 1.78 (septet of d/apparent octet, 3 JHH=7.1 Hz, 2 JPH= 14.5 Hz, 3H, P(CH(CH3)2), 2.23(septet of d/apparent octet, 3 JHH=7.3 Hz, 2 JPH= 14.5 Hz, 15 H, P(CH(CH3)2)3), 2.78(d, 3 JHH=14.8 Hz, 1H, HC=CHH), 3.06(t, 3 JHH=4.9Hz, 1H, Ar-H C8H8), 3.50(d, 3 JHH=4.9 Hz, 1H, Ar- H C8H8), 3.88(dd, 3 JHH=14.8 Hz, 3 JHH=7.9 Hz, 1H, HC=CHH), 4.25(d, 3 JHH=7.9 Hz, 1H, HC=CHH), 5.20 (overlapping m, 2H, Ar-H C8H8), 5.95(t, 3 JHH=5.8 Hz, 1H, Ar-C C8H8), 7.00 (t, 1H, para-h C8H5), 7.11(m, 2H, meta-h C8H5), 7.69 (d, 3 JHH= 7.6 Hz, 2H, ortho-h C8H5). 31 P{ 1 H} NMR(298 K, C6D6, 202.5 MHz): δ 30.3 (dd, 2 JPP=20.4, 3 JPP=1.5 Hz 1P, P(CH(CH3)2), 57.58(dd, 2 JPP=20.4, 3 JPP=5.4 Hz 1P, P(CH(CH3)2), 57.77(d, 3 JPP=1.5 Hz 1P, P(CH(CH3)2) 13 C{ 1 H} NMR (298 K, C6D6, 125.7 MHz): δ 19.9 (s, 3C, P(CH(CH3)2), 20.5(s, 3C, P(CH(CH3)2), 20.3-21.1 (4x d, 2 JPC=4.6Hz, 12C, P(CH(CH3)2), 25.8 (d, 1 JPC=14.4 Hz, 9 C, P(CH(CH3)2), 59.3(s, 1C, Ar-C C8H8), 59.6 (s, 1C, Ph-HC-CH2), 61.6 (s, 1C, Ar-C C8H8), 69.8(s, 1C, Ar-C C8H8), 74.2 (s, 1C, 8
Ar-C C8H8), 78.8 (s, 1C, Ar-C C8H8), 80.5(s, 1C, ipso-c C8H8), 89.1 (s, 1C, Ph-HC-CH2), 124.6 (s, 1C, para-c), 127.1 (s, 2C, aromatic C), 130.5 (s, 2C, aromatic C), 150.4 (d, 2 JPC= 4.0 Hz, 1C, Ni-C), 168.1(s, 1C, ipso-c C8H5), 242.4 (dd, 2 JPC= 42.3 Hz, 2 JPC= 24.7 Hz, 1C, Ni-C) Isomer B 1 H NMR (298 K, C6D6, 500 MHz): δ 19.91 (dd, 2 JPH=29.1 Hz, 2 JPH=10.9 Hz 1H, Ni-H), 14.90 (dd, 2 JPH=23.1 Hz, 3 JPH=5.6 Hz, 1H, Ni-H), 14.80 (tm, 2 JPH=16.1 Hz, 1H, Ni-H), δ 0.79-1.10 (4x dd, 3 JHH= 7.2 Hz, 3 JPH= 12.7 Hz, 36 H, P(CH(CH3)2)3), 1.42 (dd, 3 JHH= 7.1 Hz, 3 JPH= 11.8 Hz, 18 H, (CH(CH3)2)3), 1.42 (septet of d/apparent octet, 3 JHH=7.1 Hz, 2 JPH= 14.5 Hz, 3H, P(CH(CH3)2), 1.83 (septet of d/apparent octet, 3 JHH=7.3 Hz, 2 JPH= 14.5 Hz, 3H, P(CH(CH3)2), 2.23(septet of d/apparent octet, 3 JHH=7.3 Hz, 2 JPH= 14.5 Hz, 15 H, P(CH(CH3)2)3), 2.10 (d, 3 JHH=14.9Hz, 1H, HC=CHH), 2.35(d, 3 JHH=5.4 Hz, 1H, Ar-H C8H8), 3.78(t, 3 JHH=5.4 Hz, 1H, Ar-H C8H8), 3.95(d, 3 JHH=8.2 Hz, 1H, HC=CHH), 4.52(dd, 3 JHH=8.2 Hz, 3 JHH=14.9Hz, 1H, HC=CHH), 5.41 (t, 1H, 3 JHH=5.9Hz, Ar-H C8H8), 5.6(overlapping m, 2H, Ar-H C8H8), 7.00 (t, 3 JHH=7.6 Hz, 1H, para-h), 7.11(m, 2H, meta-h), 7.61 (d, 3 JHH= 7.6 Hz, 2H, ortho-h). 31 P{ 1 H} NMR(298 K, C6D6, 202.5 MHz): δ 29.4 (dd, 2 JPP=17.6 Hz, 3 JPP=2.0 Hz, 1P, P(CH(CH3)2), 56.8 (d, 3 JPP=2.0 Hz, 1P, P(CH(CH3), 58.2 (d, 2 JPP=17.6 Hz, 1P, P(CH(CH3)2) 13 C{ 1 H} NMR (298 K, C6D6, 125.7 MHz): δ 19.5 (s, 3C, P(CH(CH3)2), 20.4(s, 3C, P(CH(CH3)2), 20.3-20.9 (4x d, 2 JPC=4.6 Hz, 12C, P(CH(CH3)2), 26.0 (d, 1 JPC=14.4 Hz, 9 C, P(CH(CH3)2), 57.6 (s, 1C, Ph-HC-CH2), 61.1 (s, 1C, Ar-C C8H8), 63.3(s, 1C, Ar-C C8H8), 67.3 (s, 1C, Ar-C C8H8), 74.5 (s, 1C, Ar-C C8H8), 80.1(s, 1C, ipso-c C8H8), 81.8 (s, 1C Ar-C C8H8), 88.2(s, 1C, Ph-HC-CH2), 124.6 (s, 1C, para-c), 127.1 (s, 2C, aromatic C), 130.5 (s, 2C, aromatic C), 150.8 (d, 3 JPC= 4.0 Hz, 1C, Ni-C), 170.0(s, 1C, ipso-c C8H5), 251.9 (dd, 2 JPC= 41.9 Hz, 2 JPC= 25.0 Hz, 1C, Ni-C) Anal Calcd. for C43H79Ni5P3: %C 52.57; %H 8.10. Found %C 52.57; %H 8.24. 9
Figure 7: 1 H NMR of 3 in C6D6 Figure 8: 1 H NMR of 3 in C6D6 10
Figure 9: 1 H NMR of 3 in C6D6 11
Figure 10: 31 P{ 1 H} NMR of 3 in C6D6 12
Figure 11: APT 13 C{ 1 H} NMR of 3 13
Figure 12: APT 13 C{ 1 H} NMR of 3 14
Figure 13: APT 13 C{ 1 H} NMR of 3 15
Figure 14: HSQC 13 C{ 1 H}- 1 H NMR of 3, showing no hydrogens correlating with the C(1) and C(2) carbon atoms, labelled Y and Z in Figure S13. 16
Figure 15: Aliquot of reaction of cluster 2 with an excess of styrene. Integrals shown for ethylbenzene CH2 peak and one hydride environment of the major and minor isomers 3. These values support the production of ethylbenzene to cluster 3 in a 3:1 ratio. Reaction of 3 with P i Pr3 + H2 A solution of 3 (10 mg, 0.010 mmol) in 0.5 ml of n-pentane was added to 2 equivalents of triisopropylphosphine (3 mg, 0.020 mmol) and transferred to a J-Young tube. 1 atmosphere of dihydrogen was introduced to the J-young tube until the solution was saturated, and the reaction was left to stir for 4 h. 1 H and 31 P{ 1 H} NMR spectra were collected and showed the conversion of 3 to 2 and 1 H NMR showed the growth of peaks corresponding to toluene and ethylbenzene in a 1:1 ratio 17
Figure 16: Stacked 1 H NMR showing the addition of P i Pr3 to 3, before (top spectrum, red) and after (bottom spectrum, blue) the addition of H2 (L = i Pr3P). 18
Figure 17: Stacked 31 P{ 1 H} NMR showing the addition of P i Pr3 to 3, before (top spectrum, red) and after (bottom spectrum, blue) the addition of H2. (L = i Pr3P). Synthesis and Characterization of (4) (Ni5(P i Pr3)5(µ2-H)5(CC(Me)=CH2). To a stirring solution of [( i Pr3P)Ni]5H6 (600 mg, 0.55 mmol) in 100 ml of n-pentane at 273 K, isobutylene was introduced to the 500 ml Schlenk flask until the solution was saturated with isobutylene. The solution was stirred for 0.25 h. The head-space gas was then removed under vacuum, and the dark brown solution was filtered through a plug of Celite. The solution was concentrated by vacuum evaporation, and then cooled to 40 C for 40 hours, which afforded dark brown plates of 1. A second crop also afforded crystals of a combination of 1 and 3 according to 1 H and 31 P{ 1 H} NMR spectra. A third crop, which was also a mix of 1 and 3, was collected and a dark brown plates of 3 were isolated which were suitable for X-Ray diffraction. 1 H NMR (298 K, C6D6, 500 MHz): δ 22.05 (sextet, 2 JPH=6.5 Hz, 5 H, Ni-H), δ 1.38 (dd, 3 JHH= 7.3 Hz, 3 JPH= 13.1 19
Hz, 90 H, P(CH(CH3)2)3), δ 2.28 (septet of d/apparent octet, 3 JHH=7.1 Hz, 2 JPH= 7.5 Hz, 15 H, P(CH(CH3)2)3), 1.62-1.78 (temperature-dependent s, 1H, isobutylene =CH2), δ 2.09 (s, 3H, isobutylene CH3), 2.91 (s, 1H, isobutylene =CH2) 31 P{ 1 H} NMR(298 K, C6D6, 202.5 MHz): δ 47.3 (s, 5P, P(CH(CH3)2) Figure 18: 1 H NMR of cluster 4 generated from in situ reaction of 1 with isobutylene in C6D6 and contaminated with cluster 2. Temperature dependent proton resonance F obscured by isobutylene, see Fig S20. 20
Figure 19: 13 C{ 1 H} DEPT-Q of cluster 4 in C6D6 at 10 C, showing the positively phased =CH2 and negatively phased CH3 carbons associated with the CC(Me)=CH2 moiety. Figure 20: HSQC 13 C{ 1 H}- 1 H NMR of 4 at 10 C, showing the correlation between the C=CH2 hydrogens and the carbon at 59.1, and the CCMe hydrogens and the carbon at 33.6. 21
Figure 21: 31 P{ 1 H} NMR of cluster 4 (top, red) and selectively decoupled 31 P{ 1 H} NMR of cluster 4 with coupling to five hydrides (bottom, blue). Figure 22: Model of 31 P{ 1 H} NMR of cluster 4 with coupling to five nuclei with a coupling constant of 6.5 Hz (black) 31 P{ 1 H} NMR of cluster 4 with coupling to hydrides (blue) 22
Conversion of 4 to 2: A solution of 4 contaminated with 2 in C6D6 was monitored over a period of 16 hours. 1 H and 31 P{ 1 H} NMR spectra were collected throughout and revealed almost all of 4 had been converted to cluster 2 along with propane as an organic byproduct. The shifts corresponding to the bound isobutylene fragment also disappeared, further supporting their assignment. Figure 23: Stacked 1 H NMR showing a mixture of cluster 4 and cluster 2 immediately (blue. top) and the same solution after 16 hours (red, bottom) 23
Figure 24: Stacked 1 H NMR of the hydride region showing a mixture of cluster 4 and cluster 2 immediately (blue, top) and the same solution after 16 hours (red, bottom) Conversion of 1 to 2 in the Presence of added Functional Group Bearing Compounds: A solution of cluster 1 (22 mg, 0.02 mmol) in 0.6 ml of n-pentane was cooled to 40 C along with a separate solution of approximately 1 equivalent of: a) n-butanol (2 mg, 0.027 mmol); b) diisopropyl amine (2 mg, 0.02 mmol); c) 3-pentanone (2 mg, 0.023 mmol); d) isopropyl actetate (2 mg, 0.02 mmol); e) N,N dimethyl formamide (2 mg, 0.024 mmol); f) 3-hexyne (2 mg, 0.023 mmol); g) neopentyl chloride (3 mg, 0.028 mmol); h) benzyl chloride (3 mg, 0.024 mmol); i) propionitrile (1 mg, 0.02 mmol)] in 0.2 ml of n-pentane. The two solutions were added together at 40 C, transferred to a J-Young tube and subsequently exposed to an excess of ethylene. Samples a-f showed conversion to cluster 2 in higher than 70 % NMR yield, as determined through integration of 31 P{ 1 H} NMR spectra. Sample g formed a new cluster from the reaction of 1 with neopentyl chloride; the nature of this compound is under investigation, but the same species could be independently prepared from the reaction of 2 directly with neopentyl chloride. Methane was generated for samples a-g, and ethane was generated for samples a-e and g. In sample f, 3-hexyne 24
was converted to 3-hexene in lieu of ethane formation. Reactivity that did not result in methane formation was observed when exposing additives h and i to cluster 1, where instantaneous reaction was observed before the addition of ethylene. Table 1: Reaction of Cluster 1 and Ethylene with Various Additives Additive Hydrogenation Methane NMR Yield Product Generation of 2 a)1-butanol Ethane Yes 80.2 % Ethane Yes 82.6 % b) Diisopropylamine c) 3-Pentanone Ethane Yes 77.1 % Ethane Yes 82.3 % d) Isopropyl Acetate Ethane Yes 70.0 % e) N,N-Dimethyl formamide 3-hexene Yes 79.6 % f) 3-hexyne g) Neopentyl Chloride h) Benzyl Chloride i) Propionitrile Ethane Yes * N/A No N/A N/A No N/A *2 reacts with neopentyl chloride after being formed. 25
III Crystallographic Information Structure Solutions: General: For complexes 2, 3 and 4 hydride ligands were located in the electron density difference maps. Their positions were refined, and their thermal parameters were treated isotropically. X-ray Solution 2. Features a disorder of the Ni(1) centre, which bridges between Ni(2) and Ni(3) with 0.45887 site occupancy, between Ni(2) and Ni(4) with 0.2702 site occupancy, and between Ni(4) and Ni(5) with 0.27092 site occupancy. The isopropyl substituents C(2)-C(10) associated with P(1) were treated as two-fold disordered, with a site occupancy of 0.68367 for the sites labelled A. The isopropyl substituents C(14)-C(16) and C(17)-C(19) associated with P(2) were treated as two-fold disordered, with a site occupancies of 0.62039 and 0.54673, respectively, for the sites labelled A. The isopropyl substituents C(44)-C(46) associated with P(5) were treated as two-fold disordered, with a site occupancy of 0.75551, for the sites labelled A. The disordered i Pr groups were restrained to have similar distances to the well-behaved isopropyl group of C(32)- C(34) using the SHELX SAME command. X-ray Solution 3. The styrene -CH=CH2 group was modelled as two-fold disordered, where the opposite face of the styrene double bond associated with C(9)-C(10) is bound to Ni(4). The site occupancies for C(9A) and C(10A) were 0.6331, consistent with the solution NMR data. X-ray solution 4. There is a two-fold disorder of atoms C(2)-C(4) and Ni(1), where the location of the CH3 and =CH2 substituents are exchanged. Atoms C(2A)-C(4A) and Ni1A feature 0.81793 site occupancy. Due to the close proximity of the pairs of atoms C(2A), C(2B); C(3A), C(4B); (C4A), C(3B) and low occupancy of the B sites, the SHELX SAME command was used to constrain the geometry of C(2B)-C(3B)-C(4B) to be the same as that of C(2A)-C(3A)-C(4A). These atoms were treated anisotropically, but with the thermal parameters of the proximal pairs of atoms constrained to be identical. The isopropyl substituents associated with C(5)-C(13) on P(1) were also two-fold disordered, with a site occupancy of the A sites refined as 0.45877. 26
Figure 25: ORTEP depiction of solid-state structure of 2 with 50% probability ellipoids shown. Hydrogens and carbons on phosphine ligand and 3-site disorder on top Ni-centre omitted for clarity. Table 2. Crystal data and structure refinement for cluster 2 Identification code shelx Empirical formula C46 H109 Ni5 P5 Formula weight 1110.73 Temperature 140(2) K Wavelength 0.71073 Å Crystal system Triclinic Space group P -1 Unit cell dimensions a = 12.4070(14) Å = 87.186(3). b = 12.5366(13) Å = 89.969(3). c = 21.207(2) Å = 60.558(3). Volume 2868.0(5) Å 3 27
Z 2 Density (calculated) 1.286 Mg/m 3 Absorption coefficient 1.778 mm -1 F(000) 1200 Crystal size 0.234 x 0.162 x 0.059 mm 3 Theta range for data collection 2.886 to 28.406. Index ranges -16<=h<=16, -16<=k<=16, -28<=l<=28 Reflections collected 104450 Independent reflections 14358 [R(int) = 0.0562] Completeness to theta = 25.242 99.8 % Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 14358 / 166 / 752 Goodness-of-fit on F 2 1.014 Final R indices [I>2sigma(I)] R1 = 0.0370, wr2 = 0.0661 R indices (all data) R1 = 0.0708, wr2 = 0.0755 Extinction coefficient n/a Largest diff. peak and hole 0.748 and -0.421 e.å -3 28
Table 3. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 2. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) Ni(1A) 8982(1) 4862(1) 2421(1) 25(1) Ni(1B) 9636(4) 4528(2) 2764(1) 38(1) Ni(1C) 10229(2) 4246(2) 2592(1) 30(1) Ni(2) 8341(1) 3657(1) 3045(1) 20(1) Ni(3) 8645(1) 3306(1) 1870(1) 25(1) Ni(5) 10662(1) 2408(1) 3220(1) 25(1) Ni(4) 10971(1) 2120(1) 2053(1) 22(1) P(1) 9746(1) 6106(1) 2391(1) 26(1) P(3) 7470(1) 3433(1) 1073(1) 33(1) P(2) 6770(1) 4070(1) 3658(1) 21(1) P(5) 11779(1) 1035(1) 3964(1) 23(1) P(4) 12504(1) 1003(1) 1446(1) 30(1) C(1) 9678(2) 3156(2) 2518(1) 22(1) C(2A) 8580(7) 7662(7) 2683(3) 31(1) C(3A) 7692(6) 7565(6) 3143(3) 42(2) C(4A) 9142(8) 8380(6) 2968(4) 60(2) C(2B) 8354(18) 7368(16) 2653(7) 41(4) C(3B) 7890(14) 6958(19) 3225(6) 53(4) C(4B) 8340(20) 8570(10) 2755(6) 62(5) C(5A) 9787(15) 6413(14) 1554(9) 40(3) C(6A) 8826(6) 6206(9) 1212(3) 49(2) C(7A) 9683(13) 7631(9) 1326(4) 76(3) C(5B) 9929(15) 6552(15) 1539(8) 33(3) C(6B) 8704(7) 7076(11) 1174(3) 58(3) C(7B) 10470(10) 7410(7) 1517(4) 48(2) C(8A) 11169(6) 5579(7) 2802(3) 41(2) C(9A) 12221(6) 4531(5) 2472(4) 46(2) C(10A) 11096(7) 5159(7) 3486(3) 57(2) C(8B) 11112(8) 6250(12) 2714(4) 55(3) C(9B) 12304(8) 5372(19) 2403(5) 144(8) 29
C(10B) 11177(8) 5995(11) 3438(3) 72(3) C(11) 5860(2) 4715(2) 1022(1) 35(1) C(12) 5113(3) 4603(3) 1568(1) 56(1) C(13) 5855(3) 5928(3) 1021(2) 57(1) C(14A) 8076(6) 3269(7) 292(2) 40(2) C(15A) 7184(8) 3769(10) -277(3) 49(2) C(16A) 8956(6) 3763(9) 257(2) 45(2) C(14B) 8099(12) 3880(20) 302(5) 56(4) C(15B) 7284(12) 4245(13) -292(5) 38(3) C(16B) 8824(12) 4450(20) 359(6) 63(4) C(17A) 7059(6) 2115(5) 1185(4) 41(2) C(18A) 6295(15) 1966(18) 657(6) 56(3) C(19A) 8216(8) 895(7) 1333(5) 58(2) C(17B) 7547(7) 2050(6) 884(4) 40(2) C(18B) 6441(15) 2170(20) 495(7) 48(3) C(19B) 7726(13) 1286(11) 1498(5) 63(3) C(20) 6578(2) 2699(2) 3789(1) 27(1) C(21) 6514(3) 2185(2) 3163(1) 40(1) C(22) 5524(2) 2833(2) 4214(1) 36(1) C(23) 5213(2) 5298(2) 3359(1) 27(1) C(24) 4212(2) 5893(2) 3849(1) 39(1) C(25) 5298(2) 6295(2) 2957(1) 36(1) C(26) 6882(2) 4474(2) 4480(1) 29(1) C(27) 7917(2) 3373(2) 4856(1) 38(1) C(28) 7113(3) 5558(3) 4469(1) 44(1) C(29) 11489(2) -278(2) 3955(1) 30(1) C(30) 10125(2) 138(3) 4068(1) 42(1) C(31) 11833(2) -853(2) 3317(1) 40(1) C(32) 13465(2) 315(2) 3830(1) 30(1) C(33) 13898(3) 1260(3) 3875(1) 45(1) C(34) 14355(2) -881(2) 4195(1) 39(1) C(35) 11477(2) 1495(2) 4792(1) 29(1) C(36) 11323(3) 2771(3) 4857(1) 49(1) C(37) 12341(2) 580(3) 5308(1) 41(1) C(38) 12432(2) -283(2) 1081(1) 41(1) C(39) 12303(3) -1101(3) 1590(2) 62(1) 30
C(40) 11359(3) 178(3) 601(2) 65(1) C(41) 12513(3) 1935(3) 746(1) 54(1) C(42) 12369(4) 3154(3) 931(2) 88(1) C(43) 13564(3) 1324(3) 278(2) 77(1) C(44A) 14049(4) 165(5) 1883(3) 45(2) C(45A) 14440(10) 1037(7) 2138(4) 53(2) C(46A) 15128(4) -880(4) 1558(3) 72(2) C(44B) 14205(14) 294(13) 1611(7) 34(4) C(45B) 14380(40) 1270(20) 1920(11) 52(6) C(46B) 14626(11) -856(10) 2036(6) 44(4) 31
Table 4: Bond lengths [Å] and angles [ ] for 2 Ni(1A)-C(1) 1.872(2) Ni(1A)-P(1) 2.1854(9) Ni(1A)-Ni(2) 2.3763(7) Ni(1A)-Ni(3) 2.5250(8) Ni(1B)-C(1) 1.799(3) Ni(1B)-P(1) 2.1597(18) Ni(1B)-Ni(2) 2.406(3) Ni(1B)-Ni(5) 2.459(2) Ni(1C)-C(1) 1.816(3) Ni(1C)-P(1) 2.1230(16) Ni(1C)-Ni(5) 2.4190(16) Ni(1C)-Ni(4) 2.674(2) Ni(1C)-Ni(2) 2.929(3) Ni(2)-C(1) 1.854(2) Ni(2)-P(2) 2.1977(6) Ni(2)-Ni(5) 2.5282(5) Ni(2)-Ni(3) 2.5475(4) Ni(2)-H(4) 1.58(3) Ni(2)-H(1) 1.52(4) Ni(3)-C(1) 1.818(2) Ni(3)-P(3) 2.1809(7) Ni(3)-Ni(4) 2.5327(5) Ni(3)-H(2) 1.62(3) Ni(3)-H(1) 1.62(4) Ni(5)-C(1) 1.823(2) Ni(5)-P(5) 2.1822(7) Ni(5)-Ni(4) 2.5210(5) Ni(5)-H(4) 1.63(3) Ni(5)-H(3) 1.57(3) Ni(4)-C(1) 1.820(2) Ni(4)-P(4) 2.1886(7) Ni(4)-H(2) 1.53(3) 32
Ni(4)-H(3) 1.62(3) P(1)-C(8A) 1.764(7) P(1)-C(2B) 1.786(17) P(1)-C(5A) 1.805(19) P(1)-C(2A) 1.903(7) P(1)-C(5B) 1.912(18) P(1)-C(8B) 1.920(7) P(3)-C(17B) 1.756(6) P(3)-C(14A) 1.798(6) P(3)-C(11) 1.847(2) P(3)-C(17A) 1.959(6) P(3)-C(14B) 1.983(9) P(2)-C(20) 1.856(2) P(2)-C(26) 1.861(2) P(2)-C(23) 1.867(2) P(5)-C(29) 1.851(2) P(5)-C(32) 1.855(2) P(5)-C(35) 1.857(2) P(4)-C(41) 1.848(3) P(4)-C(38) 1.863(3) P(4)-C(44B) 1.869(16) P(4)-C(44A) 1.887(5) C(2A)-C(3A) 1.517(7) C(2A)-C(4A) 1.528(6) C(2A)-H(2A) 1.0000 C(3A)-H(3A1) 0.9800 C(3A)-H(3A2) 0.9800 C(3A)-H(3A3) 0.9800 C(4A)-H(4A1) 0.9800 C(4A)-H(4A2) 0.9800 C(4A)-H(4A3) 0.9800 C(2B)-C(3B) 1.515(12) C(2B)-C(4B) 1.524(11) C(2B)-H(2B) 1.0000 C(3B)-H(3B1) 0.9800 C(3B)-H(3B2) 0.9800 33
C(3B)-H(3B3) 0.9800 C(4B)-H(4B1) 0.9800 C(4B)-H(4B2) 0.9800 C(4B)-H(4B3) 0.9800 C(5A)-C(7A) 1.522(11) C(5A)-C(6A) 1.530(11) C(5A)-H(5A) 1.0000 C(6A)-H(6A1) 0.9800 C(6A)-H(6A2) 0.9800 C(6A)-H(6A3) 0.9800 C(7A)-H(7A1) 0.9800 C(7A)-H(7A2) 0.9800 C(7A)-H(7A3) 0.9800 C(5B)-C(6B) 1.520(12) C(5B)-C(7B) 1.522(11) C(5B)-H(5B) 1.0000 C(6B)-H(6B1) 0.9800 C(6B)-H(6B2) 0.9800 C(6B)-H(6B3) 0.9800 C(7B)-H(7B1) 0.9800 C(7B)-H(7B2) 0.9800 C(7B)-H(7B3) 0.9800 C(8A)-C(9A) 1.524(9) C(8A)-C(10A) 1.536(9) C(8A)-H(8A) 1.0000 C(9A)-H(9A1) 0.9800 C(9A)-H(9A2) 0.9800 C(9A)-H(9A3) 0.9800 C(10A)-H(10A) 0.9800 C(10A)-H(10B) 0.9800 C(10A)-H(10C) 0.9800 C(8B)-C(9B) 1.519(12) C(8B)-C(10B) 1.547(10) C(8B)-H(8B) 1.0000 C(9B)-H(9B1) 0.9800 C(9B)-H(9B2) 0.9800 34
C(9B)-H(9B3) 0.9800 C(10B)-H(10D) 0.9800 C(10B)-H(10E) 0.9800 C(10B)-H(10F) 0.9800 C(11)-C(13) 1.518(4) C(11)-C(12) 1.525(4) C(11)-H(11) 1.0000 C(12)-H(12A) 0.9800 C(12)-H(12B) 0.9800 C(12)-H(12C) 0.9800 C(13)-H(13A) 0.9800 C(13)-H(13B) 0.9800 C(13)-H(13C) 0.9800 C(14A)-C(16A) 1.497(7) C(14A)-C(15A) 1.522(7) C(14A)-H(14A) 1.0000 C(15A)-H(15A) 0.9800 C(15A)-H(15B) 0.9800 C(15A)-H(15C) 0.9800 C(16A)-H(16A) 0.9800 C(16A)-H(16B) 0.9800 C(16A)-H(16C) 0.9800 C(14B)-C(16B) 1.410(9) C(14B)-C(15B) 1.519(10) C(14B)-H(14B) 1.0000 C(15B)-H(15D) 0.9800 C(15B)-H(15E) 0.9800 C(15B)-H(15F) 0.9800 C(16B)-H(16D) 0.9800 C(16B)-H(16E) 0.9800 C(16B)-H(16F) 0.9800 C(17A)-C(19A) 1.514(9) C(17A)-C(18A) 1.542(10) C(17A)-H(17A) 1.0000 C(18A)-H(18A) 0.9800 C(18A)-H(18B) 0.9800 35
C(18A)-H(18C) 0.9800 C(19A)-H(19A) 0.9800 C(19A)-H(19B) 0.9800 C(19A)-H(19C) 0.9800 C(17B)-C(19B) 1.525(11) C(17B)-C(18B) 1.539(10) C(17B)-H(17B) 1.0000 C(18B)-H(18D) 0.9800 C(18B)-H(18E) 0.9800 C(18B)-H(18F) 0.9800 C(19B)-H(19D) 0.9800 C(19B)-H(19E) 0.9800 C(19B)-H(19F) 0.9800 C(20)-C(21) 1.523(3) C(20)-C(22) 1.532(3) C(20)-H(20) 1.0000 C(21)-H(21A) 0.9800 C(21)-H(21B) 0.9800 C(21)-H(21C) 0.9800 C(22)-H(22A) 0.9800 C(22)-H(22B) 0.9800 C(22)-H(22C) 0.9800 C(23)-C(25) 1.525(3) C(23)-C(24) 1.531(3) C(23)-H(23) 1.0000 C(24)-H(24A) 0.9800 C(24)-H(24B) 0.9800 C(24)-H(24C) 0.9800 C(25)-H(25A) 0.9800 C(25)-H(25B) 0.9800 C(25)-H(25C) 0.9800 C(26)-C(28) 1.520(3) C(26)-C(27) 1.531(3) C(26)-H(26) 1.0000 C(27)-H(27A) 0.9800 C(27)-H(27B) 0.9800 36
C(27)-H(27C) 0.9800 C(28)-H(28A) 0.9800 C(28)-H(28B) 0.9800 C(28)-H(28C) 0.9800 C(29)-C(31) 1.524(3) C(29)-C(30) 1.529(3) C(29)-H(29) 1.0000 C(30)-H(30A) 0.9800 C(30)-H(30B) 0.9800 C(30)-H(30C) 0.9800 C(31)-H(31A) 0.9800 C(31)-H(31B) 0.9800 C(31)-H(31C) 0.9800 C(32)-C(34) 1.525(3) C(32)-C(33) 1.529(3) C(32)-H(32) 1.0000 C(33)-H(33A) 0.9800 C(33)-H(33B) 0.9800 C(33)-H(33C) 0.9800 C(34)-H(34A) 0.9800 C(34)-H(34B) 0.9800 C(34)-H(34C) 0.9800 C(35)-C(37) 1.527(3) C(35)-C(36) 1.527(3) C(35)-H(35) 1.0000 C(36)-H(36A) 0.9800 C(36)-H(36B) 0.9800 C(36)-H(36C) 0.9800 C(37)-H(37A) 0.9800 C(37)-H(37B) 0.9800 C(37)-H(37C) 0.9800 C(38)-C(39) 1.514(4) C(38)-C(40) 1.527(4) C(38)-H(38) 1.0000 C(39)-H(39A) 0.9800 C(39)-H(39B) 0.9800 37
C(39)-H(39C) 0.9800 C(40)-H(40A) 0.9800 C(40)-H(40B) 0.9800 C(40)-H(40C) 0.9800 C(41)-C(42) 1.521(5) C(41)-C(43) 1.537(4) C(41)-H(41) 1.0000 C(42)-H(42A) 0.9800 C(42)-H(42B) 0.9800 C(42)-H(42C) 0.9800 C(43)-H(43A) 0.9800 C(43)-H(43B) 0.9800 C(43)-H(43C) 0.9800 C(44A)-C(45A) 1.517(7) C(44A)-C(46A) 1.532(6) C(44A)-H(44A) 1.0000 C(45A)-H(45A) 0.9800 C(45A)-H(45B) 0.9800 C(45A)-H(45C) 0.9800 C(46A)-H(46A) 0.9800 C(46A)-H(46B) 0.9800 C(46A)-H(46C) 0.9800 C(44B)-C(46B) 1.515(12) C(44B)-C(45B) 1.521(13) C(44B)-H(44B) 1.0000 C(45B)-H(45D) 0.9800 C(45B)-H(45E) 0.9800 C(45B)-H(45F) 0.9800 C(46B)-H(46D) 0.9800 C(46B)-H(46E) 0.9800 C(46B)-H(46F) 0.9800 C(1)-Ni(1A)-P(1) 134.03(8) C(1)-Ni(1A)-Ni(2) 50.04(7) P(1)-Ni(1A)-Ni(2) 147.90(5) C(1)-Ni(1A)-Ni(3) 45.94(7) 38
P(1)-Ni(1A)-Ni(3) 147.96(4) Ni(2)-Ni(1A)-Ni(3) 62.544(19) C(1)-Ni(1B)-P(1) 141.33(14) C(1)-Ni(1B)-Ni(2) 49.78(9) P(1)-Ni(1B)-Ni(2) 147.50(18) C(1)-Ni(1B)-Ni(5) 47.66(8) P(1)-Ni(1B)-Ni(5) 149.88(19) Ni(2)-Ni(1B)-Ni(5) 62.61(4) C(1)-Ni(1C)-P(1) 143.02(13) C(1)-Ni(1C)-Ni(5) 48.46(8) P(1)-Ni(1C)-Ni(5) 158.19(12) C(1)-Ni(1C)-Ni(4) 42.71(8) P(1)-Ni(1C)-Ni(4) 142.67(11) Ni(5)-Ni(1C)-Ni(4) 59.09(4) C(1)-Ni(1C)-Ni(2) 37.50(9) P(1)-Ni(1C)-Ni(2) 119.57(12) Ni(5)-Ni(1C)-Ni(2) 55.44(5) Ni(4)-Ni(1C)-Ni(2) 79.97(4) C(1)-Ni(2)-P(2) 174.21(7) C(1)-Ni(2)-Ni(1A) 50.70(7) P(2)-Ni(2)-Ni(1A) 134.63(3) C(1)-Ni(2)-Ni(1B) 47.81(9) P(2)-Ni(2)-Ni(1B) 137.89(7) C(1)-Ni(2)-Ni(5) 46.05(7) P(2)-Ni(2)-Ni(5) 133.09(2) Ni(1A)-Ni(2)-Ni(5) 79.57(2) Ni(1B)-Ni(2)-Ni(5) 59.71(8) C(1)-Ni(2)-Ni(3) 45.50(7) P(2)-Ni(2)-Ni(3) 132.40(2) Ni(1A)-Ni(2)-Ni(3) 61.59(2) Ni(1B)-Ni(2)-Ni(3) 77.35(5) Ni(5)-Ni(2)-Ni(3) 88.941(13) C(1)-Ni(2)-Ni(1C) 36.62(8) P(2)-Ni(2)-Ni(1C) 148.99(5) Ni(5)-Ni(2)-Ni(1C) 52.00(4) Ni(3)-Ni(2)-Ni(1C) 70.37(4) 39
C(1)-Ni(2)-H(4) 84.0(12) P(2)-Ni(2)-H(4) 96.4(12) Ni(1A)-Ni(2)-H(4) 99.6(12) Ni(1B)-Ni(2)-H(4) 75.5(12) Ni(5)-Ni(2)-H(4) 38.9(12) Ni(3)-Ni(2)-H(4) 127.9(12) Ni(1C)-Ni(2)-H(4) 74.5(12) C(1)-Ni(2)-H(1) 81.3(14) P(2)-Ni(2)-H(1) 98.0(14) Ni(1A)-Ni(2)-H(1) 72.5(14) Ni(1B)-Ni(2)-H(1) 95.9(14) Ni(5)-Ni(2)-H(1) 126.2(14) Ni(3)-Ni(2)-H(1) 37.3(14) Ni(1C)-Ni(2)-H(1) 94.5(14) H(4)-Ni(2)-H(1) 165.1(18) C(1)-Ni(3)-P(3) 177.75(7) C(1)-Ni(3)-Ni(1A) 47.71(7) P(3)-Ni(3)-Ni(1A) 133.55(3) C(1)-Ni(3)-Ni(4) 45.91(7) P(3)-Ni(3)-Ni(4) 131.84(2) Ni(1A)-Ni(3)-Ni(4) 79.42(2) C(1)-Ni(3)-Ni(2) 46.65(7) P(3)-Ni(3)-Ni(2) 135.40(2) Ni(1A)-Ni(3)-Ni(2) 55.87(2) Ni(4)-Ni(3)-Ni(2) 90.428(13) C(1)-Ni(3)-H(2) 81.2(10) P(3)-Ni(3)-H(2) 96.6(10) Ni(1A)-Ni(3)-H(2) 105.5(9) Ni(4)-Ni(3)-H(2) 35.3(10) Ni(2)-Ni(3)-H(2) 124.8(10) C(1)-Ni(3)-H(1) 79.8(13) P(3)-Ni(3)-H(1) 102.4(13) Ni(1A)-Ni(3)-H(1) 66.8(13) Ni(4)-Ni(3)-H(1) 124.9(13) Ni(2)-Ni(3)-H(1) 34.6(13) H(2)-Ni(3)-H(1) 159.3(17) 40
C(1)-Ni(5)-P(5) 162.08(7) C(1)-Ni(5)-Ni(1C) 48.22(8) P(5)-Ni(5)-Ni(1C) 148.40(5) C(1)-Ni(5)-Ni(1B) 46.83(8) P(5)-Ni(5)-Ni(1B) 150.97(5) C(1)-Ni(5)-Ni(4) 46.16(7) P(5)-Ni(5)-Ni(4) 124.83(2) Ni(1C)-Ni(5)-Ni(4) 65.50(6) Ni(1B)-Ni(5)-Ni(4) 77.25(6) C(1)-Ni(5)-Ni(2) 47.07(7) P(5)-Ni(5)-Ni(2) 130.98(2) Ni(1C)-Ni(5)-Ni(2) 72.56(6) Ni(1B)-Ni(5)-Ni(2) 57.69(9) Ni(4)-Ni(5)-Ni(2) 91.139(13) C(1)-Ni(5)-H(4) 83.6(11) P(5)-Ni(5)-H(4) 99.7(11) Ni(1C)-Ni(5)-H(4) 90.7(11) Ni(1B)-Ni(5)-H(4) 73.2(11) Ni(4)-Ni(5)-H(4) 128.7(11) Ni(2)-Ni(5)-H(4) 37.5(11) C(1)-Ni(5)-H(3) 83.4(12) P(5)-Ni(5)-H(3) 92.7(12) Ni(1C)-Ni(5)-H(3) 80.6(11) Ni(1B)-Ni(5)-H(3) 97.6(11) Ni(4)-Ni(5)-H(3) 38.7(12) Ni(2)-Ni(5)-H(3) 129.7(12) H(4)-Ni(5)-H(3) 167.0(16) C(1)-Ni(4)-P(4) 175.40(7) C(1)-Ni(4)-Ni(5) 46.26(7) P(4)-Ni(4)-Ni(5) 136.60(2) C(1)-Ni(4)-Ni(3) 45.85(7) P(4)-Ni(4)-Ni(3) 132.73(2) Ni(5)-Ni(4)-Ni(3) 89.433(13) C(1)-Ni(4)-Ni(1C) 42.61(9) P(4)-Ni(4)-Ni(1C) 134.17(6) Ni(5)-Ni(4)-Ni(1C) 55.41(5) 41
Ni(3)-Ni(4)-Ni(1C) 74.98(5) C(1)-Ni(4)-H(2) 83.5(10) P(4)-Ni(4)-H(2) 95.1(10) Ni(5)-Ni(4)-H(2) 125.8(10) Ni(3)-Ni(4)-H(2) 37.7(10) Ni(1C)-Ni(4)-H(2) 104.3(10) C(1)-Ni(4)-H(3) 82.2(11) P(4)-Ni(4)-H(3) 100.0(11) Ni(5)-Ni(4)-H(3) 37.3(11) Ni(3)-Ni(4)-H(3) 126.7(11) Ni(1C)-Ni(4)-H(3) 71.8(11) H(2)-Ni(4)-H(3) 162.0(16) C(8A)-P(1)-C(5A) 114.5(5) C(8A)-P(1)-C(2A) 108.7(3) C(5A)-P(1)-C(2A) 103.5(6) C(2B)-P(1)-C(5B) 105.9(7) C(2B)-P(1)-C(8B) 107.6(7) C(5B)-P(1)-C(8B) 94.1(4) C(2B)-P(1)-Ni(1B) 103.1(5) C(5B)-P(1)-Ni(1B) 129.4(4) C(8B)-P(1)-Ni(1B) 115.2(4) C(8A)-P(1)-Ni(1A) 116.2(3) C(5A)-P(1)-Ni(1A) 102.3(4) C(2A)-P(1)-Ni(1A) 110.8(2) C(17B)-P(3)-C(11) 111.3(3) C(14A)-P(3)-C(11) 107.30(19) C(14A)-P(3)-C(17A) 104.2(4) C(11)-P(3)-C(17A) 96.6(2) C(17B)-P(3)-C(14B) 102.5(7) C(11)-P(3)-C(14B) 98.6(5) C(17B)-P(3)-Ni(3) 115.6(2) C(14A)-P(3)-Ni(3) 118.7(3) C(11)-P(3)-Ni(3) 118.31(8) C(17A)-P(3)-Ni(3) 108.59(18) C(14B)-P(3)-Ni(3) 107.7(3) C(20)-P(2)-C(26) 102.33(11) 42
C(20)-P(2)-C(23) 103.92(11) C(26)-P(2)-C(23) 104.26(11) C(20)-P(2)-Ni(2) 110.37(7) C(26)-P(2)-Ni(2) 117.40(8) C(23)-P(2)-Ni(2) 116.81(7) C(29)-P(5)-C(32) 102.98(11) C(29)-P(5)-C(35) 103.32(11) C(32)-P(5)-C(35) 109.09(11) C(29)-P(5)-Ni(5) 109.72(8) C(32)-P(5)-Ni(5) 112.92(8) C(35)-P(5)-Ni(5) 117.42(8) C(41)-P(4)-C(38) 102.11(14) C(41)-P(4)-C(44B) 94.1(4) C(38)-P(4)-C(44B) 100.8(5) C(41)-P(4)-C(44A) 112.9(2) C(38)-P(4)-C(44A) 101.53(19) C(41)-P(4)-Ni(4) 110.35(9) C(38)-P(4)-Ni(4) 116.07(9) C(44B)-P(4)-Ni(4) 128.7(5) C(44A)-P(4)-Ni(4) 113.17(16) Ni(1B)-C(1)-Ni(3) 117.84(15) Ni(1C)-C(1)-Ni(3) 121.48(13) Ni(1B)-C(1)-Ni(4) 118.43(17) Ni(1C)-C(1)-Ni(4) 94.68(14) Ni(3)-C(1)-Ni(4) 88.24(9) Ni(1B)-C(1)-Ni(5) 85.51(12) Ni(1C)-C(1)-Ni(5) 83.32(10) Ni(3)-C(1)-Ni(5) 155.11(13) Ni(4)-C(1)-Ni(5) 87.58(10) Ni(1B)-C(1)-Ni(2) 82.41(14) Ni(1C)-C(1)-Ni(2) 105.88(14) Ni(3)-C(1)-Ni(2) 87.85(10) Ni(4)-C(1)-Ni(2) 157.91(13) Ni(5)-C(1)-Ni(2) 86.88(9) Ni(3)-C(1)-Ni(1A) 86.34(10) Ni(4)-C(1)-Ni(1A) 122.15(12) 43
Ni(5)-C(1)-Ni(1A) 116.42(11) Ni(2)-C(1)-Ni(1A) 79.26(9) C(3A)-C(2A)-C(4A) 109.6(5) C(3A)-C(2A)-P(1) 111.9(4) C(4A)-C(2A)-P(1) 115.1(5) C(3A)-C(2A)-H(2A) 106.5 C(4A)-C(2A)-H(2A) 106.5 P(1)-C(2A)-H(2A) 106.5 C(2A)-C(3A)-H(3A1) 109.5 C(2A)-C(3A)-H(3A2) 109.5 H(3A1)-C(3A)-H(3A2) 109.5 C(2A)-C(3A)-H(3A3) 109.5 H(3A1)-C(3A)-H(3A3) 109.5 H(3A2)-C(3A)-H(3A3) 109.5 C(2A)-C(4A)-H(4A1) 109.5 C(2A)-C(4A)-H(4A2) 109.5 H(4A1)-C(4A)-H(4A2) 109.5 C(2A)-C(4A)-H(4A3) 109.5 H(4A1)-C(4A)-H(4A3) 109.5 H(4A2)-C(4A)-H(4A3) 109.5 C(3B)-C(2B)-C(4B) 111.3(11) C(3B)-C(2B)-P(1) 109.9(10) C(4B)-C(2B)-P(1) 118.5(10) C(3B)-C(2B)-H(2B) 105.3 C(4B)-C(2B)-H(2B) 105.3 P(1)-C(2B)-H(2B) 105.3 C(2B)-C(3B)-H(3B1) 109.5 C(2B)-C(3B)-H(3B2) 109.5 H(3B1)-C(3B)-H(3B2) 109.5 C(2B)-C(3B)-H(3B3) 109.5 H(3B1)-C(3B)-H(3B3) 109.5 H(3B2)-C(3B)-H(3B3) 109.5 C(2B)-C(4B)-H(4B1) 109.5 C(2B)-C(4B)-H(4B2) 109.5 H(4B1)-C(4B)-H(4B2) 109.5 C(2B)-C(4B)-H(4B3) 109.5 44
H(4B1)-C(4B)-H(4B3) 109.5 H(4B2)-C(4B)-H(4B3) 109.5 C(7A)-C(5A)-C(6A) 110.6(9) C(7A)-C(5A)-P(1) 118.6(11) C(6A)-C(5A)-P(1) 109.2(10) C(7A)-C(5A)-H(5A) 105.9 C(6A)-C(5A)-H(5A) 105.9 P(1)-C(5A)-H(5A) 105.9 C(5A)-C(6A)-H(6A1) 109.5 C(5A)-C(6A)-H(6A2) 109.5 H(6A1)-C(6A)-H(6A2) 109.5 C(5A)-C(6A)-H(6A3) 109.5 H(6A1)-C(6A)-H(6A3) 109.5 H(6A2)-C(6A)-H(6A3) 109.5 C(5A)-C(7A)-H(7A1) 109.5 C(5A)-C(7A)-H(7A2) 109.5 H(7A1)-C(7A)-H(7A2) 109.5 C(5A)-C(7A)-H(7A3) 109.5 H(7A1)-C(7A)-H(7A3) 109.5 H(7A2)-C(7A)-H(7A3) 109.5 C(6B)-C(5B)-C(7B) 113.1(10) C(6B)-C(5B)-P(1) 110.1(10) C(7B)-C(5B)-P(1) 111.0(9) C(6B)-C(5B)-H(5B) 107.5 C(7B)-C(5B)-H(5B) 107.5 P(1)-C(5B)-H(5B) 107.5 C(5B)-C(6B)-H(6B1) 109.5 C(5B)-C(6B)-H(6B2) 109.5 H(6B1)-C(6B)-H(6B2) 109.5 C(5B)-C(6B)-H(6B3) 109.5 H(6B1)-C(6B)-H(6B3) 109.5 H(6B2)-C(6B)-H(6B3) 109.5 C(5B)-C(7B)-H(7B1) 109.5 C(5B)-C(7B)-H(7B2) 109.5 H(7B1)-C(7B)-H(7B2) 109.5 C(5B)-C(7B)-H(7B3) 109.5 45
H(7B1)-C(7B)-H(7B3) 109.5 H(7B2)-C(7B)-H(7B3) 109.5 C(9A)-C(8A)-C(10A) 109.8(6) C(9A)-C(8A)-P(1) 111.1(5) C(10A)-C(8A)-P(1) 110.6(5) C(9A)-C(8A)-H(8A) 108.4 C(10A)-C(8A)-H(8A) 108.4 P(1)-C(8A)-H(8A) 108.4 C(8A)-C(9A)-H(9A1) 109.5 C(8A)-C(9A)-H(9A2) 109.5 H(9A1)-C(9A)-H(9A2) 109.5 C(8A)-C(9A)-H(9A3) 109.5 H(9A1)-C(9A)-H(9A3) 109.5 H(9A2)-C(9A)-H(9A3) 109.5 C(8A)-C(10A)-H(10A) 109.5 C(8A)-C(10A)-H(10B) 109.5 H(10A)-C(10A)-H(10B) 109.5 C(8A)-C(10A)-H(10C) 109.5 H(10A)-C(10A)-H(10C) 109.5 H(10B)-C(10A)-H(10C) 109.5 C(9B)-C(8B)-C(10B) 112.3(8) C(9B)-C(8B)-P(1) 110.6(6) C(10B)-C(8B)-P(1) 107.1(5) C(9B)-C(8B)-H(8B) 108.9 C(10B)-C(8B)-H(8B) 108.9 P(1)-C(8B)-H(8B) 108.9 C(8B)-C(9B)-H(9B1) 109.5 C(8B)-C(9B)-H(9B2) 109.5 H(9B1)-C(9B)-H(9B2) 109.5 C(8B)-C(9B)-H(9B3) 109.5 H(9B1)-C(9B)-H(9B3) 109.5 H(9B2)-C(9B)-H(9B3) 109.5 C(8B)-C(10B)-H(10D) 109.5 C(8B)-C(10B)-H(10E) 109.5 H(10D)-C(10B)-H(10E) 109.5 C(8B)-C(10B)-H(10F) 109.5 46
H(10D)-C(10B)-H(10F) 109.5 H(10E)-C(10B)-H(10F) 109.5 C(13)-C(11)-C(12) 110.7(2) C(13)-C(11)-P(3) 109.80(19) C(12)-C(11)-P(3) 110.74(19) C(13)-C(11)-H(11) 108.5 C(12)-C(11)-H(11) 108.5 P(3)-C(11)-H(11) 108.5 C(11)-C(12)-H(12A) 109.5 C(11)-C(12)-H(12B) 109.5 H(12A)-C(12)-H(12B) 109.5 C(11)-C(12)-H(12C) 109.5 H(12A)-C(12)-H(12C) 109.5 H(12B)-C(12)-H(12C) 109.5 C(11)-C(13)-H(13A) 109.5 C(11)-C(13)-H(13B) 109.5 H(13A)-C(13)-H(13B) 109.5 C(11)-C(13)-H(13C) 109.5 H(13A)-C(13)-H(13C) 109.5 H(13B)-C(13)-H(13C) 109.5 C(16A)-C(14A)-C(15A) 109.8(5) C(16A)-C(14A)-P(3) 109.2(4) C(15A)-C(14A)-P(3) 119.3(5) C(16A)-C(14A)-H(14A) 105.9 C(15A)-C(14A)-H(14A) 105.9 P(3)-C(14A)-H(14A) 105.9 C(14A)-C(15A)-H(15A) 109.5 C(14A)-C(15A)-H(15B) 109.5 H(15A)-C(15A)-H(15B) 109.5 C(14A)-C(15A)-H(15C) 109.5 H(15A)-C(15A)-H(15C) 109.5 H(15B)-C(15A)-H(15C) 109.5 C(14A)-C(16A)-H(16A) 109.5 C(14A)-C(16A)-H(16B) 109.5 H(16A)-C(16A)-H(16B) 109.5 C(14A)-C(16A)-H(16C) 109.5 47
H(16A)-C(16A)-H(16C) 109.5 H(16B)-C(16A)-H(16C) 109.5 C(16B)-C(14B)-C(15B) 115.7(8) C(16B)-C(14B)-P(3) 119.4(7) C(15B)-C(14B)-P(3) 116.7(7) C(16B)-C(14B)-H(14B) 99.6 C(15B)-C(14B)-H(14B) 99.6 P(3)-C(14B)-H(14B) 99.6 C(14B)-C(15B)-H(15D) 109.5 C(14B)-C(15B)-H(15E) 109.5 H(15D)-C(15B)-H(15E) 109.5 C(14B)-C(15B)-H(15F) 109.5 H(15D)-C(15B)-H(15F) 109.5 H(15E)-C(15B)-H(15F) 109.5 C(14B)-C(16B)-H(16D) 109.5 C(14B)-C(16B)-H(16E) 109.5 H(16D)-C(16B)-H(16E) 109.5 C(14B)-C(16B)-H(16F) 109.5 H(16D)-C(16B)-H(16F) 109.5 H(16E)-C(16B)-H(16F) 109.5 C(19A)-C(17A)-C(18A) 109.1(9) C(19A)-C(17A)-P(3) 110.6(6) C(18A)-C(17A)-P(3) 118.3(6) C(19A)-C(17A)-H(17A) 106.0 C(18A)-C(17A)-H(17A) 106.0 P(3)-C(17A)-H(17A) 106.0 C(17A)-C(18A)-H(18A) 109.5 C(17A)-C(18A)-H(18B) 109.5 H(18A)-C(18A)-H(18B) 109.5 C(17A)-C(18A)-H(18C) 109.5 H(18A)-C(18A)-H(18C) 109.5 H(18B)-C(18A)-H(18C) 109.5 C(17A)-C(19A)-H(19A) 109.5 C(17A)-C(19A)-H(19B) 109.5 H(19A)-C(19A)-H(19B) 109.5 C(17A)-C(19A)-H(19C) 109.5 48
H(19A)-C(19A)-H(19C) 109.5 H(19B)-C(19A)-H(19C) 109.5 C(19B)-C(17B)-C(18B) 110.4(8) C(19B)-C(17B)-P(3) 108.2(6) C(18B)-C(17B)-P(3) 115.8(9) C(19B)-C(17B)-H(17B) 107.4 C(18B)-C(17B)-H(17B) 107.4 P(3)-C(17B)-H(17B) 107.4 C(17B)-C(18B)-H(18D) 109.5 C(17B)-C(18B)-H(18E) 109.5 H(18D)-C(18B)-H(18E) 109.5 C(17B)-C(18B)-H(18F) 109.5 H(18D)-C(18B)-H(18F) 109.5 H(18E)-C(18B)-H(18F) 109.5 C(17B)-C(19B)-H(19D) 109.5 C(17B)-C(19B)-H(19E) 109.5 H(19D)-C(19B)-H(19E) 109.5 C(17B)-C(19B)-H(19F) 109.5 H(19D)-C(19B)-H(19F) 109.5 H(19E)-C(19B)-H(19F) 109.5 C(21)-C(20)-C(22) 110.9(2) C(21)-C(20)-P(2) 110.79(17) C(22)-C(20)-P(2) 116.88(16) C(21)-C(20)-H(20) 105.8 C(22)-C(20)-H(20) 105.8 P(2)-C(20)-H(20) 105.8 C(20)-C(21)-H(21A) 109.5 C(20)-C(21)-H(21B) 109.5 H(21A)-C(21)-H(21B) 109.5 C(20)-C(21)-H(21C) 109.5 H(21A)-C(21)-H(21C) 109.5 H(21B)-C(21)-H(21C) 109.5 C(20)-C(22)-H(22A) 109.5 C(20)-C(22)-H(22B) 109.5 H(22A)-C(22)-H(22B) 109.5 C(20)-C(22)-H(22C) 109.5 49
H(22A)-C(22)-H(22C) 109.5 H(22B)-C(22)-H(22C) 109.5 C(25)-C(23)-C(24) 109.38(19) C(25)-C(23)-P(2) 111.67(17) C(24)-C(23)-P(2) 116.93(17) C(25)-C(23)-H(23) 106.0 C(24)-C(23)-H(23) 106.0 P(2)-C(23)-H(23) 106.0 C(23)-C(24)-H(24A) 109.5 C(23)-C(24)-H(24B) 109.5 H(24A)-C(24)-H(24B) 109.5 C(23)-C(24)-H(24C) 109.5 H(24A)-C(24)-H(24C) 109.5 H(24B)-C(24)-H(24C) 109.5 C(23)-C(25)-H(25A) 109.5 C(23)-C(25)-H(25B) 109.5 H(25A)-C(25)-H(25B) 109.5 C(23)-C(25)-H(25C) 109.5 H(25A)-C(25)-H(25C) 109.5 H(25B)-C(25)-H(25C) 109.5 C(28)-C(26)-C(27) 110.3(2) C(28)-C(26)-P(2) 110.04(16) C(27)-C(26)-P(2) 110.51(16) C(28)-C(26)-H(26) 108.7 C(27)-C(26)-H(26) 108.7 P(2)-C(26)-H(26) 108.7 C(26)-C(27)-H(27A) 109.5 C(26)-C(27)-H(27B) 109.5 H(27A)-C(27)-H(27B) 109.5 C(26)-C(27)-H(27C) 109.5 H(27A)-C(27)-H(27C) 109.5 H(27B)-C(27)-H(27C) 109.5 C(26)-C(28)-H(28A) 109.5 C(26)-C(28)-H(28B) 109.5 H(28A)-C(28)-H(28B) 109.5 C(26)-C(28)-H(28C) 109.5 50
H(28A)-C(28)-H(28C) 109.5 H(28B)-C(28)-H(28C) 109.5 C(31)-C(29)-C(30) 109.0(2) C(31)-C(29)-P(5) 109.70(17) C(30)-C(29)-P(5) 110.72(17) C(31)-C(29)-H(29) 109.1 C(30)-C(29)-H(29) 109.1 P(5)-C(29)-H(29) 109.1 C(29)-C(30)-H(30A) 109.5 C(29)-C(30)-H(30B) 109.5 H(30A)-C(30)-H(30B) 109.5 C(29)-C(30)-H(30C) 109.5 H(30A)-C(30)-H(30C) 109.5 H(30B)-C(30)-H(30C) 109.5 C(29)-C(31)-H(31A) 109.5 C(29)-C(31)-H(31B) 109.5 H(31A)-C(31)-H(31B) 109.5 C(29)-C(31)-H(31C) 109.5 H(31A)-C(31)-H(31C) 109.5 H(31B)-C(31)-H(31C) 109.5 C(34)-C(32)-C(33) 110.7(2) C(34)-C(32)-P(5) 119.62(17) C(33)-C(32)-P(5) 110.36(18) C(34)-C(32)-H(32) 104.9 C(33)-C(32)-H(32) 104.9 P(5)-C(32)-H(32) 104.9 C(32)-C(33)-H(33A) 109.5 C(32)-C(33)-H(33B) 109.5 H(33A)-C(33)-H(33B) 109.5 C(32)-C(33)-H(33C) 109.5 H(33A)-C(33)-H(33C) 109.5 H(33B)-C(33)-H(33C) 109.5 C(32)-C(34)-H(34A) 109.5 C(32)-C(34)-H(34B) 109.5 H(34A)-C(34)-H(34B) 109.5 C(32)-C(34)-H(34C) 109.5 51
H(34A)-C(34)-H(34C) 109.5 H(34B)-C(34)-H(34C) 109.5 C(37)-C(35)-C(36) 111.6(2) C(37)-C(35)-P(5) 117.44(18) C(36)-C(35)-P(5) 111.33(17) C(37)-C(35)-H(35) 105.1 C(36)-C(35)-H(35) 105.1 P(5)-C(35)-H(35) 105.1 C(35)-C(36)-H(36A) 109.5 C(35)-C(36)-H(36B) 109.5 H(36A)-C(36)-H(36B) 109.5 C(35)-C(36)-H(36C) 109.5 H(36A)-C(36)-H(36C) 109.5 H(36B)-C(36)-H(36C) 109.5 C(35)-C(37)-H(37A) 109.5 C(35)-C(37)-H(37B) 109.5 H(37A)-C(37)-H(37B) 109.5 C(35)-C(37)-H(37C) 109.5 H(37A)-C(37)-H(37C) 109.5 H(37B)-C(37)-H(37C) 109.5 C(39)-C(38)-C(40) 109.5(3) C(39)-C(38)-P(4) 109.85(18) C(40)-C(38)-P(4) 112.0(2) C(39)-C(38)-H(38) 108.5 C(40)-C(38)-H(38) 108.5 P(4)-C(38)-H(38) 108.5 C(38)-C(39)-H(39A) 109.5 C(38)-C(39)-H(39B) 109.5 H(39A)-C(39)-H(39B) 109.5 C(38)-C(39)-H(39C) 109.5 H(39A)-C(39)-H(39C) 109.5 H(39B)-C(39)-H(39C) 109.5 C(38)-C(40)-H(40A) 109.5 C(38)-C(40)-H(40B) 109.5 H(40A)-C(40)-H(40B) 109.5 C(38)-C(40)-H(40C) 109.5 52
H(40A)-C(40)-H(40C) 109.5 H(40B)-C(40)-H(40C) 109.5 C(42)-C(41)-C(43) 110.9(3) C(42)-C(41)-P(4) 111.2(2) C(43)-C(41)-P(4) 118.0(2) C(42)-C(41)-H(41) 105.2 C(43)-C(41)-H(41) 105.2 P(4)-C(41)-H(41) 105.2 C(41)-C(42)-H(42A) 109.5 C(41)-C(42)-H(42B) 109.5 H(42A)-C(42)-H(42B) 109.5 C(41)-C(42)-H(42C) 109.5 H(42A)-C(42)-H(42C) 109.5 H(42B)-C(42)-H(42C) 109.5 C(41)-C(43)-H(43A) 109.5 C(41)-C(43)-H(43B) 109.5 H(43A)-C(43)-H(43B) 109.5 C(41)-C(43)-H(43C) 109.5 H(43A)-C(43)-H(43C) 109.5 H(43B)-C(43)-H(43C) 109.5 C(45A)-C(44A)-C(46A) 110.7(6) C(45A)-C(44A)-P(4) 112.3(5) C(46A)-C(44A)-P(4) 117.9(4) C(45A)-C(44A)-H(44A) 104.9 C(46A)-C(44A)-H(44A) 104.9 P(4)-C(44A)-H(44A) 104.9 C(44A)-C(45A)-H(45A) 109.5 C(44A)-C(45A)-H(45B) 109.5 H(45A)-C(45A)-H(45B) 109.5 C(44A)-C(45A)-H(45C) 109.5 H(45A)-C(45A)-H(45C) 109.5 H(45B)-C(45A)-H(45C) 109.5 C(44A)-C(46A)-H(46A) 109.5 C(44A)-C(46A)-H(46B) 109.5 H(46A)-C(46A)-H(46B) 109.5 C(44A)-C(46A)-H(46C) 109.5 53
H(46A)-C(46A)-H(46C) 109.5 H(46B)-C(46A)-H(46C) 109.5 C(46B)-C(44B)-C(45B) 112.7(12) C(46B)-C(44B)-P(4) 108.8(9) C(45B)-C(44B)-P(4) 105.8(17) C(46B)-C(44B)-H(44B) 109.8 C(45B)-C(44B)-H(44B) 109.8 P(4)-C(44B)-H(44B) 109.8 C(44B)-C(45B)-H(45D) 109.5 C(44B)-C(45B)-H(45E) 109.5 H(45D)-C(45B)-H(45E) 109.5 C(44B)-C(45B)-H(45F) 109.5 H(45D)-C(45B)-H(45F) 109.5 H(45E)-C(45B)-H(45F) 109.5 C(44B)-C(46B)-H(46D) 109.5 C(44B)-C(46B)-H(46E) 109.5 H(46D)-C(46B)-H(46E) 109.5 C(44B)-C(46B)-H(46F) 109.5 H(46D)-C(46B)-H(46F) 109.5 H(46E)-C(46B)-H(46F) 109.5 Symmetry transformations used to generate equivalent atoms: 54
Figure 26: ORTEP depicition of solid-state structure of 3 with 50% probability ellipoids shown. Carbons and hydrogens on phosphine ligands along with 2-site disorder on the bound vinylic carbons ommited for clarity Table 5: Crystal data and structure refinement for 3 Identification code shelx Empirical formula C43 H79 Ni5 P3 Formula weight 982.52 Temperature 134(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P 21 Unit cell dimensions a = 9.2461(7) Å = 90. b = 21.8005(19) Å = 99.603(3). c = 11.6957(10) Å = 90. Volume 2324.5(3) Å 3 Z 2 Density (calculated) 1.404 Mg/m 3 Absorption coefficient 2.119 mm -1 F(000) 1044 Crystal size? x? x? mm 3 55
Theta range for data collection 2.913 to 27.500. Index ranges -12<=h<=12, -28<=k<=28, -15<=l<=15 Reflections collected 101108 Independent reflections 10672 [R(int) = 0.0470] Completeness to theta = 27.500 99.9 % Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 10672 / 1 / 510 Goodness-of-fit on F 2 1.131 Final R indices [I>2sigma(I)] R1 = 0.0288, wr2 = 0.0464 R indices (all data) R1 = 0.0356, wr2 = 0.0488 Absolute structure parameter 0.092(11) Extinction coefficient n/a Largest diff. peak and hole 0.324 and -0.303 e.å -3 56
Table 6: Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for shelx. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) NI1 1131(1) 3485(1) 2635(1) 15(1) NI2 110(1) 4751(1) -91(1) 15(1) NI3 1475(1) 5302(1) 1623(1) 15(1) NI4 48(1) 4647(1) 2680(1) 16(1) NI5-509(1) 3831(1) 1039(1) 14(1) P(1) 3122(1) 3228(1) 3802(1) 15(1) P(2) -769(1) 4967(1) -1865(1) 18(1) P(3) 2224(1) 6236(1) 1954(1) 19(1) C(1) 1052(4) 4468(2) 1419(3) 15(1) C(2) 1685(4) 3893(2) 1315(3) 14(1) C(3) 2729(4) 3740(2) 538(3) 15(1) C(4) 3674(4) 4184(2) 219(3) 22(1) C(5) 4630(5) 4043(2) -540(4) 32(1) C(6) 4649(5) 3462(2) -1001(4) 32(1) C(7) 3718(5) 3017(2) -701(4) 28(1) C(8) 2771(4) 3154(2) 70(3) 22(1) C(9A) -743(8) 4892(3) 4171(6) 26(2) C(10A) -1780(11) 4621(5) 3313(9) 24(2) C(9B) -1689(14) 5026(8) 3341(13) 34(4) C(10B) -1394(17) 4458(9) 3776(15) 27(4) C(11) -1548(4) 3973(2) 2936(4) 28(1) C(12) -2423(4) 3846(2) 1822(4) 22(1) C(13) -2244(4) 3305(2) 1234(4) 22(1) C(14) -1079(4) 2911(2) 1719(4) 24(1) C(15) -522(4) 2938(2) 2947(4) 31(1) C(16) -720(4) 3476(3) 3538(4) 34(1) C(17) 4530(4) 2844(2) 3093(4) 21(1) C(18) 3946(5) 2267(2) 2421(4) 30(1) C(19) 6007(5) 2708(2) 3843(4) 31(1) C(20) 4111(4) 3903(2) 4504(4) 23(1) C(21) 4633(5) 4323(2) 3603(4) 28(1) 57
C(22) 3128(5) 4266(2) 5184(4) 30(1) C(23) 2803(5) 2753(2) 5075(4) 25(1) C(24) 2461(5) 2083(2) 4750(4) 33(1) C(25) 3976(6) 2781(2) 6162(4) 40(1) C(26) -708(5) 4301(2) -2869(4) 27(1) C(27) -2086(5) 3896(2) -3023(4) 36(1) C(28) 625(5) 3902(2) -2440(4) 29(1) C(29) -2750(5) 5181(2) -2109(4) 29(1) C(30) -3352(6) 5437(2) -3313(4) 39(1) C(31) -3140(5) 5581(2) -1140(4) 37(1) C(32) 123(5) 5576(2) -2621(4) 28(1) C(33) 1727(6) 5414(2) -2647(5) 41(1) C(34) 42(6) 6194(2) -2034(4) 34(1) C(35) 950(5) 6806(2) 1155(4) 25(1) C(36) -660(5) 6629(2) 1141(5) 38(1) C(37) 1259(6) 7477(2) 1493(4) 35(1) C(38) 4020(5) 6420(2) 1496(4) 29(1) C(39) 3867(6) 6578(2) 208(4) 40(1) C(40) 5074(6) 5877(3) 1754(5) 46(1) C(41) 2537(5) 6516(2) 3484(4) 26(1) C(42) 3664(6) 6120(2) 4259(4) 37(1) C(43) 1120(5) 6534(2) 3985(4) 39(1) 58
Table 7: Bond lengths [Å] and angles [ ] for 3 NI1-C(9) 1.935(4) NI1-P(1) 2.1499(11) NI1-NI2 2.4913(7) NI1-NI5 2.5210(7) NI1-H(1) 1.60(4) NI1-H(2) 1.67(6) NI2-C(9) 1.867(4) NI2-P(2) 2.1650(11) NI2-NI4 2.4189(7) NI2-H(2) 1.60(5) NI2-H(3) 1.49(4) NI3-C(10) 1.924(4) NI3-C(7) 2.020(4) NI3-C(8) 2.156(4) NI3-P(3) 2.1747(11) NI3-NI5 2.3256(7) NI3-C(6) 2.483(4) NI3-NI4 2.7279(7) NI4-C(9) 1.910(4) NI4-C(1A) 1.956(9) NI4-C(1B) 2.039(15) NI4-C(2B) 2.066(13) NI4-C(2A) 2.070(6) NI4-C(3) 2.139(4) NI4-NI5 2.6054(7) NI4-H(3) 1.56(4) NI5-C(9) 1.999(4) NI5-C(10) 2.005(3) NI5-C(5) 2.014(4) NI5-C(4) 2.124(4) NI5-C(6) 2.252(4) 59
NI5-H(1) 1.62(4) P(1)-C(20) 1.862(4) P(1)-C(23) 1.864(4) P(1)-C(17) 1.875(4) P(2)-C(26) 1.854(4) P(2)-C(32) 1.866(4) P(2)-C(29) 1.872(4) P(3)-C(35) 1.851(4) P(3)-C(38) 1.856(4) P(3)-C(41) 1.876(4) C(1Aa)-C(2A) 1.398(14) C(1Aa)-C(3) 1.506(12) C(1Aa)-H(1A) 0.9500 C(2Aa)-H(2A) 0.9500 C(2Aa)-H(2B) 0.9500 C(1Bb)-C(2B) 1.35(3) C(1Bb)-C(3) 1.435(17) C(1Bb)-H(1B) 0.9500 C(2Bb)-H(2C) 0.9500 C(2Bb)-H(2D) 0.9500 C(3)-C(8) 1.440(7) C(3)-C(4) 1.442(6) C(4)-C(5) 1.387(6) C(4)-H(4) 0.9500 C(5)-C(6) 1.421(6) C(5)-H(5) 0.9500 C(6)-C(7) 1.444(6) C(6)-H(6) 0.9500 C(7)-C(8) 1.389(7) C(7)-H(7) 0.9500 C(8)-H(8) 0.9500 C(9)-C(10) 1.397(5) C(10)-C(11) 1.470(5) C(11)-C(12) 1.393(5) C(11)-C(16) 1.395(6) C(12)-C(13) 1.390(6) 60
C(12)-H(12) 0.9500 C(13)-C(14) 1.381(7) C(13)-H(13) 0.9500 C(14)-C(15) 1.377(7) C(14)-H(14) 0.9500 C(15)-C(16) 1.389(6) C(15)-H(15) 0.9500 C(16)-H(16) 0.9500 C(17)-C(18) 1.523(6) C(17)-C(19) 1.537(6) C(17)-H(17) 1.0000 C(18)-H(18A) 0.9800 C(18)-H(18B) 0.9800 C(18)-H(18C) 0.9800 C(19)-H(19A) 0.9800 C(19)-H(19B) 0.9800 C(19)-H(19C) 0.9800 C(20)-C(21) 1.521(6) C(20)-C(22) 1.530(7) C(20)-H(20) 1.0000 C(21)-H(21A) 0.9800 C(21)-H(21B) 0.9800 C(21)-H(21C) 0.9800 C(22)-H(22A) 0.9800 C(22)-H(22B) 0.9800 C(22)-H(22C) 0.9800 C(23)-C(24) 1.521(6) C(23)-C(25) 1.532(6) C(23)-H(23) 1.0000 C(24)-H(24A) 0.9800 C(24)-H(24B) 0.9800 C(24)-H(24C) 0.9800 C(25)-H(25A) 0.9800 C(25)-H(25B) 0.9800 C(25)-H(25C) 0.9800 C(26)-C(28) 1.532(6) 61
C(26)-C(27) 1.535(6) C(26)-H(26) 1.0000 C(27)-H(27A) 0.9800 C(27)-H(27B) 0.9800 C(27)-H(27C) 0.9800 C(28)-H(28A) 0.9800 C(28)-H(28B) 0.9800 C(28)-H(28C) 0.9800 C(29)-C(30) 1.528(7) C(29)-C(31) 1.530(7) C(29)-H(29) 1.0000 C(30)-H(30A) 0.9800 C(30)-H(30B) 0.9800 C(30)-H(30C) 0.9800 C(31)-H(31A) 0.9800 C(31)-H(31B) 0.9800 C(31)-H(31C) 0.9800 C(32)-C(33) 1.523(6) C(32)-C(34) 1.530(6) C(32)-H(32) 1.0000 C(33)-H(33A) 0.9800 C(33)-H(33B) 0.9800 C(33)-H(33C) 0.9800 C(34)-H(34A) 0.9800 C(34)-H(34B) 0.9800 C(34)-H(34C) 0.9800 C(35)-C(37) 1.525(6) C(35)-C(36) 1.533(6) C(35)-H(35) 1.0000 C(36)-H(36A) 0.9800 C(36)-H(36B) 0.9800 C(36)-H(36C) 0.9800 C(37)-H(37A) 0.9800 C(37)-H(37B) 0.9800 C(37)-H(37C) 0.9800 C(38)-C(40) 1.524(6) 62
C(38)-C(39) 1.533(6) C(38)-H(38) 1.0000 C(39)-H(39A) 0.9800 C(39)-H(39B) 0.9800 C(39)-H(39C) 0.9800 C(40)-H(40A) 0.9800 C(40)-H(40B) 0.9800 C(40)-H(40C) 0.9800 C(41)-C(42) 1.529(6) C(41)-C(43) 1.529(6) C(41)-H(41) 1.0000 C(42)-H(42A) 0.9800 C(42)-H(42B) 0.9800 C(42)-H(42C) 0.9800 C(43)-H(43A) 0.9800 C(43)-H(43B) 0.9800 C(43)-H(43C) 0.9800 C(9)-NI1-P(1) 172.04(12) C(9)-NI1-NI2 47.88(11) P(1)-NI1-NI2 136.89(4) C(9)-NI1-NI5 51.28(11) P(1)-NI1-NI5 126.70(4) NI2-NI1-NI5 95.20(2) C(9)-NI1-H(1) 89.8(16) P(1)-NI1-H(1) 88.1(16) NI2-NI1-H(1) 132.2(16) NI5-NI1-H(1) 38.7(16) C(9)-NI1-H(2) 82.7(19) P(1)-NI1-H(2) 99.8(19) NI2-NI1-H(2) 39.4(18) NI5-NI1-H(2) 133.5(19) H(1)-NI1-H(2) 172(3) C(9)-NI2-P(2) 173.18(12) C(9)-NI2-NI4 50.97(12) P(2)-NI2-NI4 130.48(4) 63
C(9)-NI2-NI1 50.27(11) P(2)-NI2-NI1 134.52(4) NI4-NI2-NI1 83.15(2) C(9)-NI2-H(2) 87(2) P(2)-NI2-H(2) 96(2) NI4-NI2-H(2) 124(2) NI1-NI2-H(2) 41(2) C(9)-NI2-H(3) 81.2(17) P(2)-NI2-H(3) 97.4(17) NI4-NI2-H(3) 38.5(17) NI1-NI2-H(3) 121.6(17) H(2)-NI2-H(3) 162(3) C(10)-NI3-C(7) 136.79(17) C(10)-NI3-C(8) 137.45(17) C(7)-NI3-C(8) 38.70(19) C(10)-NI3-P(3) 108.19(11) C(7)-NI3-P(3) 108.75(13) C(8)-NI3-P(3) 110.38(12) C(10)-NI3-NI5 55.34(10) C(7)-NI3-NI5 85.66(12) C(8)-NI3-NI5 86.07(12) P(3)-NI3-NI5 163.32(4) C(10)-NI3-C(6) 101.37(14) C(7)-NI3-C(6) 35.56(16) C(8)-NI3-C(6) 62.81(16) P(3)-NI3-C(6) 133.69(10) NI5-NI3-C(6) 55.75(10) C(10)-NI3-NI4 74.56(11) C(7)-NI3-NI4 104.70(14) C(8)-NI3-NI4 71.03(15) P(3)-NI3-NI4 120.17(3) NI5-NI3-NI4 61.461(19) C(6)-NI3-NI4 101.43(10) C(9)-NI4-C(1A) 148.1(3) C(9)-NI4-C(1B) 153.8(5) C(9)-NI4-C(2B) 151.5(5) 64
C(1Bb)-NI4-C(2B) 38.3(7) C(9)-NI4-C(2A) 171.4(2) C(1Aa)-NI4-C(2A) 40.5(4) C(9)-NI4-C(3) 113.78(16) C(1Aa)-NI4-C(3) 42.9(3) C(1Bb)-NI4-C(3) 40.1(5) C(2Bb)-NI4-C(3) 68.0(5) C(2Aa)-NI4-C(3) 73.1(2) C(9)-NI4-NI2 49.39(11) C(1Aa)-NI4-NI2 142.2(3) C(1Bb)-NI4-NI2 155.5(5) C(2Bb)-NI4-NI2 118.7(5) C(2Aa)-NI4-NI2 125.32(19) C(3)-NI4-NI2 157.67(12) C(9)-NI4-NI5 49.69(11) C(1Aa)-NI4-NI5 100.5(3) C(1Bb)-NI4-NI5 104.8(5) C(2Bb)-NI4-NI5 118.6(4) C(2Aa)-NI4-NI5 137.9(2) C(3)-NI4-NI5 65.01(12) NI2-NI4-NI5 94.83(2) C(9)-NI4-NI3 64.39(11) C(1Aa)-NI4-NI3 108.8(3) C(1Bb)-NI4-NI3 96.0(6) C(2Bb)-NI4-NI3 133.5(5) C(2Aa)-NI4-NI3 116.0(2) C(3)-NI4-NI3 68.18(12) NI2-NI4-NI3 107.75(2) NI5-NI4-NI3 51.643(17) C(9)-NI4-H(3) 78.0(16) C(1Aa)-NI4-H(3) 129.3(16) C(1Bb)-NI4-H(3) 127.6(17) C(2Bb)-NI4-H(3) 105.7(17) C(2Aa)-NI4-H(3) 94.5(16) C(3)-NI4-H(3) 166.0(16) NI2-NI4-H(3) 36.3(16) 65
NI5-NI4-H(3) 127.6(16) NI3-NI4-H(3) 113.3(16) C(9)-NI5-C(10) 40.82(15) C(9)-NI5-C(5) 158.26(16) C(10)-NI5-C(5) 145.49(16) C(9)-NI5-C(4) 121.07(16) C(10)-NI5-C(4) 145.37(15) C(5)-NI5-C(4) 39.06(16) C(9)-NI5-C(6) 138.00(15) C(10)-NI5-C(6) 107.10(15) C(5)-NI5-C(6) 38.39(15) C(4)-NI5-C(6) 66.45(16) C(9)-NI5-NI3 72.34(11) C(10)-NI5-NI3 52.12(10) C(5)-NI5-NI3 98.64(12) C(4)-NI5-NI3 97.90(11) C(6)-NI5-NI3 65.66(11) C(9)-NI5-NI1 49.05(11) C(10)-NI5-NI1 73.62(11) C(5)-NI5-NI1 140.04(12) C(4)-NI5-NI1 119.48(12) C(6)-NI5-NI1 168.85(11) NI3-NI5-NI1 120.27(2) C(9)-NI5-NI4 46.76(11) C(10)-NI5-NI4 76.38(10) C(5)-NI5-NI4 111.61(13) C(4)-NI5-NI4 75.42(12) C(6)-NI5-NI4 112.17(11) NI3-NI5-NI4 66.90(2) NI1-NI5-NI4 78.93(2) C(9)-NI5-H(1) 87.1(15) C(10)-NI5-H(1) 102.1(15) C(5)-NI5-H(1) 105.8(15) C(4)-NI5-H(1) 106.2(16) C(6)-NI5-H(1) 132.9(15) NI3-NI5-H(1) 154.2(15) 66
NI1-NI5-H(1) 38.2(15) NI4-NI5-H(1) 110.1(15) C(20)-P(1)-C(23) 104.5(2) C(20)-P(1)-C(17) 101.05(19) C(23)-P(1)-C(17) 103.2(2) C(20)-P(1)-NI1 119.22(14) C(23)-P(1)-NI1 113.96(14) C(17)-P(1)-NI1 112.90(14) C(26)-P(2)-C(32) 104.4(2) C(26)-P(2)-C(29) 103.4(2) C(32)-P(2)-C(29) 101.6(2) C(26)-P(2)-NI2 112.47(14) C(32)-P(2)-NI2 118.23(14) C(29)-P(2)-NI2 115.03(14) C(35)-P(3)-C(38) 103.04(18) C(35)-P(3)-C(41) 102.64(19) C(38)-P(3)-C(41) 108.69(19) C(35)-P(3)-NI3 112.14(14) C(38)-P(3)-NI3 114.78(14) C(41)-P(3)-NI3 114.30(14) C(2Aa)-C(1Aa)-C(3) 119.5(8) C(2Aa)-C(1Aa)-NI4 74.2(5) C(3)-C(1Aa)-NI4 75.1(4) C(2Aa)-C(1Aa)-H(1A) 120.3 C(3)-C(1Aa)-H(1A) 120.3 NI4-C(1Aa)-H(1A) 121.8 C(1Aa)-C(2Aa)-NI4 65.3(5) C(1Aa)-C(2Aa)-H(2A) 120.0 NI4-C(2Aa)-H(2A) 80.8 C(1Aa)-C(2Aa)-H(2B) 120.0 NI4-C(2Aa)-H(2B) 125.2 H(2Aa)-C(2Aa)-H(2B) 120.0 C(2Bb)-C(1Bb)-C(3) 115.3(15) C(2Bb)-C(1Bb)-NI4 71.9(9) C(3)-C(1Bb)-NI4 73.7(6) C(2Bb)-C(1Bb)-H(1B) 122.3 67
C(3)-C(1Bb)-H(1B) 122.3 NI4-C(1Bb)-H(1B) 123.5 C(1Bb)-C(2Bb)-NI4 69.7(9) C(1Bb)-C(2Bb)-H(2C) 120.0 NI4-C(2Bb)-H(2C) 77.4 C(1Bb)-C(2Bb)-H(2D) 120.0 NI4-C(2Bb)-H(2D) 124.3 H(2Cb)-C(2Bb)-H(2D) 120.0 C(1Bb)-C(3)-C(8) 103.7(9) C(1Bb)-C(3)-C(4) 137.5(9) C(8)-C(3)-C(4) 118.0(4) C(8)-C(3)-C(1A) 130.7(6) C(4)-C(3)-C(1A) 111.0(5) C(1Bb)-C(3)-NI4 66.2(7) C(8)-C(3)-NI4 105.2(3) C(4)-C(3)-NI4 107.5(3) C(1Aa)-C(3)-NI4 62.1(4) C(5)-C(4)-C(3) 121.1(4) C(5)-C(4)-NI5 66.2(2) C(3)-C(4)-NI5 90.6(2) C(5)-C(4)-H(4) 119.5 C(3)-C(4)-H(4) 119.5 NI5-C(4)-H(4) 113.5 C(4)-C(5)-C(6) 117.5(4) C(4)-C(5)-NI5 74.7(2) C(6)-C(5)-NI5 79.9(2) C(4)-C(5)-H(5) 121.3 C(6)-C(5)-H(5) 121.3 NI5-C(5)-H(5) 115.0 C(5)-C(6)-C(7) 119.6(4) C(5)-C(6)-NI5 61.7(2) C(7)-C(6)-NI5 104.4(3) C(5)-C(6)-NI3 112.4(3) C(7)-C(6)-NI3 54.5(2) NI5-C(6)-NI3 58.59(9) C(5)-C(6)-H(6) 120.2 68
C(7)-C(6)-H(6) 120.2 NI5-C(6)-H(6) 102.9 NI3-C(6)-H(6) 101.5 C(8)-C(7)-C(6) 118.3(4) C(8)-C(7)-NI3 75.9(3) C(6)-C(7)-NI3 90.0(3) C(8)-C(7)-H(7) 120.8 C(6)-C(7)-H(7) 120.8 NI3-C(7)-H(7) 103.7 C(7)-C(8)-C(3) 119.7(4) C(7)-C(8)-NI3 65.4(2) C(3)-C(8)-NI3 98.9(3) C(7)-C(8)-H(8) 120.2 C(3)-C(8)-H(8) 120.2 NI3-C(8)-H(8) 105.1 C(10)-C(9)-NI2 143.4(3) C(10)-C(9)-NI4 121.0(3) NI2-C(9)-NI4 79.65(15) C(10)-C(9)-NI1 109.8(3) NI2-C(9)-NI1 81.86(15) NI4-C(9)-NI1 115.88(19) C(10)-C(9)-NI5 69.8(2) NI2-C(9)-NI5 146.4(2) NI4-C(9)-NI5 83.55(14) NI1-C(9)-NI5 79.67(13) C(9)-C(10)-C(11) 125.8(3) C(9)-C(10)-NI3 100.0(3) C(11)-C(10)-NI3 132.9(3) C(9)-C(10)-NI5 69.4(2) C(11)-C(10)-NI5 129.5(3) NI3-C(10)-NI5 72.54(12) C(12)-C(11)-C(16) 118.2(4) C(12)-C(11)-C(10) 121.0(3) C(16)-C(11)-C(10) 120.8(4) C(13)-C(12)-C(11) 120.9(4) C(13)-C(12)-H(12) 119.5 69
C(11)-C(12)-H(12) 119.5 C(14)-C(13)-C(12) 120.0(4) C(14)-C(13)-H(13) 120.0 C(12)-C(13)-H(13) 120.0 C(15)-C(14)-C(13) 119.8(4) C(15)-C(14)-H(14) 120.1 C(13)-C(14)-H(14) 120.1 C(14)-C(15)-C(16) 120.4(4) C(14)-C(15)-H(15) 119.8 C(16)-C(15)-H(15) 119.8 C(15)-C(16)-C(11) 120.7(4) C(15)-C(16)-H(16) 119.7 C(11)-C(16)-H(16) 119.7 C(18)-C(17)-C(19) 108.6(3) C(18)-C(17)-P(1) 110.0(3) C(19)-C(17)-P(1) 114.0(3) C(18)-C(17)-H(17) 108.0 C(19)-C(17)-H(17) 108.0 P(1)-C(17)-H(17) 108.0 C(17)-C(18)-H(18A) 109.5 C(17)-C(18)-H(18B) 109.5 H(18A)-C(18)-H(18B) 109.5 C(17)-C(18)-H(18C) 109.5 H(18A)-C(18)-H(18C) 109.5 H(18B)-C(18)-H(18C) 109.5 C(17)-C(19)-H(19A) 109.5 C(17)-C(19)-H(19B) 109.5 H(19A)-C(19)-H(19B) 109.5 C(17)-C(19)-H(19C) 109.5 H(19A)-C(19)-H(19C) 109.5 H(19B)-C(19)-H(19C) 109.5 C(21)-C(20)-C(22) 109.5(4) C(21)-C(20)-P(1) 111.0(3) C(22)-C(20)-P(1) 110.7(3) C(21)-C(20)-H(20) 108.5 C(22)-C(20)-H(20) 108.5 70
P(1)-C(20)-H(20) 108.5 C(20)-C(21)-H(21A) 109.5 C(20)-C(21)-H(21B) 109.5 H(21A)-C(21)-H(21B) 109.5 C(20)-C(21)-H(21C) 109.5 H(21A)-C(21)-H(21C) 109.5 H(21B)-C(21)-H(21C) 109.5 C(20)-C(22)-H(22A) 109.5 C(20)-C(22)-H(22B) 109.5 H(22A)-C(22)-H(22B) 109.5 C(20)-C(22)-H(22C) 109.5 H(22A)-C(22)-H(22C) 109.5 H(22B)-C(22)-H(22C) 109.5 C(24)-C(23)-C(25) 112.4(4) C(24)-C(23)-P(1) 112.2(3) C(25)-C(23)-P(1) 115.4(3) C(24)-C(23)-H(23) 105.2 C(25)-C(23)-H(23) 105.2 P(1)-C(23)-H(23) 105.2 C(23)-C(24)-H(24A) 109.5 C(23)-C(24)-H(24B) 109.5 H(24A)-C(24)-H(24B) 109.5 C(23)-C(24)-H(24C) 109.5 H(24A)-C(24)-H(24C) 109.5 H(24B)-C(24)-H(24C) 109.5 C(23)-C(25)-H(25A) 109.5 C(23)-C(25)-H(25B) 109.5 H(25A)-C(25)-H(25B) 109.5 C(23)-C(25)-H(25C) 109.5 H(25A)-C(25)-H(25C) 109.5 H(25B)-C(25)-H(25C) 109.5 C(28)-C(26)-C(27) 112.4(4) C(28)-C(26)-P(2) 115.8(3) C(27)-C(26)-P(2) 111.8(3) C(28)-C(26)-H(26) 105.3 C(27)-C(26)-H(26) 105.3 71
P(2)-C(26)-H(26) 105.3 C(26)-C(27)-H(27A) 109.5 C(26)-C(27)-H(27B) 109.5 H(27A)-C(27)-H(27B) 109.5 C(26)-C(27)-H(27C) 109.5 H(27A)-C(27)-H(27C) 109.5 H(27B)-C(27)-H(27C) 109.5 C(26)-C(28)-H(28A) 109.5 C(26)-C(28)-H(28B) 109.5 H(28A)-C(28)-H(28B) 109.5 C(26)-C(28)-H(28C) 109.5 H(28A)-C(28)-H(28C) 109.5 H(28B)-C(28)-H(28C) 109.5 C(30)-C(29)-C(31) 108.7(4) C(30)-C(29)-P(2) 112.9(3) C(31)-C(29)-P(2) 110.1(3) C(30)-C(29)-H(29) 108.3 C(31)-C(29)-H(29) 108.3 P(2)-C(29)-H(29) 108.3 C(29)-C(30)-H(30A) 109.5 C(29)-C(30)-H(30B) 109.5 H(30A)-C(30)-H(30B) 109.5 C(29)-C(30)-H(30C) 109.5 H(30A)-C(30)-H(30C) 109.5 H(30B)-C(30)-H(30C) 109.5 C(29)-C(31)-H(31A) 109.5 C(29)-C(31)-H(31B) 109.5 H(31A)-C(31)-H(31B) 109.5 C(29)-C(31)-H(31C) 109.5 H(31A)-C(31)-H(31C) 109.5 H(31B)-C(31)-H(31C) 109.5 C(33)-C(32)-C(34) 109.3(4) C(33)-C(32)-P(2) 111.8(3) C(34)-C(32)-P(2) 111.4(3) C(33)-C(32)-H(32) 108.1 C(34)-C(32)-H(32) 108.1 72
P(2)-C(32)-H(32) 108.1 C(32)-C(33)-H(33A) 109.5 C(32)-C(33)-H(33B) 109.5 H(33A)-C(33)-H(33B) 109.5 C(32)-C(33)-H(33C) 109.5 H(33A)-C(33)-H(33C) 109.5 H(33B)-C(33)-H(33C) 109.5 C(32)-C(34)-H(34A) 109.5 C(32)-C(34)-H(34B) 109.5 H(34A)-C(34)-H(34B) 109.5 C(32)-C(34)-H(34C) 109.5 H(34A)-C(34)-H(34C) 109.5 H(34B)-C(34)-H(34C) 109.5 C(37)-C(35)-C(36) 109.4(4) C(37)-C(35)-P(3) 110.5(3) C(36)-C(35)-P(3) 111.0(3) C(37)-C(35)-H(35) 108.6 C(36)-C(35)-H(35) 108.6 P(3)-C(35)-H(35) 108.6 C(35)-C(36)-H(36A) 109.5 C(35)-C(36)-H(36B) 109.5 H(36A)-C(36)-H(36B) 109.5 C(35)-C(36)-H(36C) 109.5 H(36A)-C(36)-H(36C) 109.5 H(36B)-C(36)-H(36C) 109.5 C(35)-C(37)-H(37A) 109.5 C(35)-C(37)-H(37B) 109.5 H(37A)-C(37)-H(37B) 109.5 C(35)-C(37)-H(37C) 109.5 H(37A)-C(37)-H(37C) 109.5 H(37B)-C(37)-H(37C) 109.5 C(40)-C(38)-C(39) 109.9(4) C(40)-C(38)-P(3) 117.3(3) C(39)-C(38)-P(3) 112.7(3) C(40)-C(38)-H(38) 105.3 C(39)-C(38)-H(38) 105.3 73
P(3)-C(38)-H(38) 105.3 C(38)-C(39)-H(39A) 109.5 C(38)-C(39)-H(39B) 109.5 H(39A)-C(39)-H(39B) 109.5 C(38)-C(39)-H(39C) 109.5 H(39A)-C(39)-H(39C) 109.5 H(39B)-C(39)-H(39C) 109.5 C(38)-C(40)-H(40A) 109.5 C(38)-C(40)-H(40B) 109.5 H(40A)-C(40)-H(40B) 109.5 C(38)-C(40)-H(40C) 109.5 H(40A)-C(40)-H(40C) 109.5 H(40B)-C(40)-H(40C) 109.5 C(42)-C(41)-C(43) 109.5(4) C(42)-C(41)-P(3) 112.5(3) C(43)-C(41)-P(3) 117.0(3) C(42)-C(41)-H(41) 105.6 C(43)-C(41)-H(41) 105.6 P(3)-C(41)-H(41) 105.6 C(41)-C(42)-H(42A) 109.5 C(41)-C(42)-H(42B) 109.5 H(42A)-C(42)-H(42B) 109.5 C(41)-C(42)-H(42C) 109.5 H(42A)-C(42)-H(42C) 109.5 H(42B)-C(42)-H(42C) 109.5 C(41)-C(43)-H(43A) 109.5 C(41)-C(43)-H(43B) 109.5 H(43A)-C(43)-H(43B) 109.5 C(41)-C(43)-H(43C) 109.5 H(43A)-C(43)-H(43C) 109.5 H(43B)-C(43)-H(43C) 109.5 Symmetry transformations used to generate equivalent atoms: 74
Figure 27: ORTEP depiction of solid-state structure of 4 with 50% probability ellipoids shown. Carbons and hydrogens on phosphine ligands along with two-site disorder on both the top Ni centre and the bound isobutylene fragment omitted for clarity. 75