Compound 3

(iPr3P)3Ni5(μ2-H)3(CCPh)(H2C=CHPh)

From: Cooperative carbon-atom abstraction from alkenes in the core of a pentanuclear nickel cluster

| 1H NMR | 31P{1H} NMR | APT 13C{1H} | HSQC | ChemDraw

Compound data: CIF

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

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 [(iPr3P)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 1H NMR (298 K, C6D6, 500 MHz): δ −21.12 (dd, 2JPH=30.2 Hz, 2JPH=10.3 Hz 1H, Ni-H), −15.77 (tm, 2JPH=15.4 Hz, 1H, Ni-H), −13.90 (d, 2JPH=22.4 Hz, 1H, Ni-H), 0.79-1.02 (4x dd, 3JHH= 7.2 Hz, 3JPH= 13.6 Hz, 36 H, P(CH(CH3)2)3), 1.42 (dd, 3JHH= 7.1 Hz, 3JPH= 12.7 Hz, 18 H, (CH(CH3)2)3­­), 1.42 (septet of d/apparent octet, 3JHH=7.1 Hz, 2JPH= 14.5 Hz, 3H, P(CH(CH3)2), 1.78 (septet of d/apparent octet, 3JHH=7.1 Hz, 2JPH= 14.5 Hz, 3H, P(CH(CH3)2), 2.23(septet of d/apparent octet, 3JHH=7.3 Hz, 2JPH= 14.5 Hz, 15 H, P(CH(CH3)2)3), 2.78(d, 3JHH=14.8 Hz, 1H, HC=CHH), 3.06(t, 3JHH=4.9Hz, 1H, Ar-H C8H8), 3.50(d, 3JHH=4.9 Hz, 1H, Ar-H C8H8), 3.88(dd, 3JHH=14.8 Hz, 3JHH=7.9 Hz, 1H, HC=CHH), 4.25(d, 3JHH=7.9 Hz, 1H, HC=CHH), 5.20 (overlapping m, 2H, Ar-H C8H8), 5.95(t,3JHH=5.8 Hz, 1H, Ar-C C8H8), 7.00 (t, 1H, para-H C8H5), 7.11(m, 2H, meta-H C8H5), 7.69 (d, 3JHH= 7.6 Hz, 2H, ortho-H C8H5). 31P{1H} NMR(298 K, C6D6, 202.5 MHz): δ 30.3 (dd, 2JPP=20.4, 3JPP=1.5 Hz 1P, P(CH(CH3)2), 57.58(dd, 2JPP=20.4, 3JPP=5.4 Hz 1P, P(CH(CH3)2), 57.77(d, 3JPP=1.5 Hz 1P, P(CH(CH3)2) 13C{1H} 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, 2JPC=4.6Hz, 12C, P(CH(CH3)2), 25.8 (d, 1JPC=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, 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, 2JPC­­­= 4.0 Hz, 1C, Ni-C), 168.1(s, 1C, ipso-C C8H5), 242.4 (dd, 2JPC­­­= 42.3 Hz, 2JPC­­­= 24.7 Hz, 1C, Ni-C) Isomer B 1H NMR (298 K, C6D6, 500 MHz): δ −19.91 (dd, 2JPH=29.1 Hz, 2JPH=10.9 Hz 1H, Ni-H), −14.90 (dd, 2JPH=23.1 Hz, 3JPH=5.6 Hz, 1H, Ni-H), −14.80 (tm, 2JPH=16.1 Hz, 1H, Ni-H), δ 0.79-1.10 (4x dd, 3JHH= 7.2 Hz, 3JPH= 12.7 Hz, 36 H, P(CH(CH3)2)3), 1.42 (dd, 3JHH= 7.1 Hz, 3JPH= 11.8 Hz, 18 H, (CH(CH3)2)3­­), 1.42 (septet of d/apparent octet, 3JHH=7.1 Hz, 2JPH= 14.5 Hz, 3H, P(CH(CH3)2), 1.83 (septet of d/apparent octet, 3JHH=7.3 Hz, 2JPH= 14.5 Hz, 3H, P(CH(CH3)2), 2.23(septet of d/apparent octet, 3JHH=7.3 Hz, 2JPH= 14.5 Hz, 15 H, P(CH(CH3)2)3), 2.10 (d, 3JHH=14.9Hz, 1H, HC=CHH), 2.35(d, 3JHH=5.4 Hz, 1H, Ar-H C8H8), 3.78(t, 3JHH=5.4 Hz, 1H, Ar-H C8H8), 3.95(d, 3JHH=8.2 Hz, 1H, HC=CHH), 4.52(dd, 3JHH=8.2 Hz, 3JHH=14.9Hz, 1H, HC=CHH), 5.41 (t, 1H, 3JHH=5.9Hz, Ar-H C8H8), 5.6(overlapping m, 2H, Ar-H C8H8), 7.00 (t, 3JHH=7.6 Hz, 1H, para-H), 7.11(m, 2H, meta-H), 7.61 (d, 3JHH= 7.6 Hz, 2H, ortho-H). 31P{1H} NMR(298 K, C6D6, 202.5 MHz): δ 29.4 (dd, 2JPP=17.6 Hz, 3JPP=2.0 Hz, 1P, P(CH(CH3)2), 56.8 (d, 3JPP=2.0 Hz, 1P, P(CH(CH3), 58.2 (d, 2JPP=17.6 Hz, 1P, P(CH(CH3)2) 13C{1H} 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, 2JPC=4.6 Hz, 12C, P(CH(CH3)2), 26.0 (d, 1JPC=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, 3JPC­­­= 4.0 Hz, 1C, Ni-C), 170.0(s, 1C, ipso-C C8H5), 251.9 (dd, 2JPC­­­= 41.9 Hz, 2JPC­­­= 25.0 Hz, 1C, Ni-C) Anal Calcd. for C43H79Ni5P3: %C 52.57; %H 8.10. Found %C 52.57; %H 8.24.

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