TY - JOUR
T1 - Synthesis and characterisation of the tetranuclear phosphinidene clusters [os3MH2(CO)12(PR)] (M = Os, R = Ph or cyclo-C6H11; M = Ru, R = cyclo-C6H11) and the crystal and molecular structure of [os4(μ-H)2(CO)12(μ3-PC 6H11)]
AU - Colbran, Stephen B.
AU - Johnson, Brian F.G.
AU - Lahoz, Fernando J.
AU - Lewis, Jack
AU - Raithby, Paul R.
PY - 1988/12/31
Y1 - 1988/12/31
N2 - Reaction of the phosphinidene-capped cluster [Os3H2(CO)9(PR)] (R = Ph or cyclo-C6H11) with the binary carbonyl [M3(CO)12] (M = Ru or Os), under reflux in nonane, affords the tetranuclear clusters [Os3MH2(CO)12(PR)] [(1) M = Os, R = Ph; (2) M = Os, R = cyclo-C6H11; (3) M = Ru, R = cyclo-C6H11] together with the previously reported penta- and hexa-nuclear clusters [Os3M2(CO)15(PR)] and [Os3M3(CO)17(PR)]. The structure of (2) has been established by an X-ray analysis which shows that there are two independent but structurally similar tetranuclear clusters per asymmetric unit. Within each molecule the four Os atoms adopt a 'butterfly' arrangement, consistent with the 62-electron count, and the phosphinidene ligand bridges an open triangular face defined by one 'bridge' and two 'wingtip' Os atoms. The 12 carbonyl ligands are terminal, and the two hydrides bridge the two remaining 'hinge' to 'wingtip' Os-Os edges. Solution 1H and 31P n.m.r. spectra for clusters (1)-(3) are consistent with this ground-state structure, and the positions of the hydrides are confirmed by the observation of 187Os satellites in the 1H n.m.r. spectra of (1) and (2). The cluster (3) exists as a mixture of three inseparable isomers which arise from the juxtaposition of the Ru atom around the three inequivalent positions of the metal 'butterfly'. The existence of these isomers is confirmed by a detailed analysis of the 1H and 31P n.m.r. spectra of this complex.
AB - Reaction of the phosphinidene-capped cluster [Os3H2(CO)9(PR)] (R = Ph or cyclo-C6H11) with the binary carbonyl [M3(CO)12] (M = Ru or Os), under reflux in nonane, affords the tetranuclear clusters [Os3MH2(CO)12(PR)] [(1) M = Os, R = Ph; (2) M = Os, R = cyclo-C6H11; (3) M = Ru, R = cyclo-C6H11] together with the previously reported penta- and hexa-nuclear clusters [Os3M2(CO)15(PR)] and [Os3M3(CO)17(PR)]. The structure of (2) has been established by an X-ray analysis which shows that there are two independent but structurally similar tetranuclear clusters per asymmetric unit. Within each molecule the four Os atoms adopt a 'butterfly' arrangement, consistent with the 62-electron count, and the phosphinidene ligand bridges an open triangular face defined by one 'bridge' and two 'wingtip' Os atoms. The 12 carbonyl ligands are terminal, and the two hydrides bridge the two remaining 'hinge' to 'wingtip' Os-Os edges. Solution 1H and 31P n.m.r. spectra for clusters (1)-(3) are consistent with this ground-state structure, and the positions of the hydrides are confirmed by the observation of 187Os satellites in the 1H n.m.r. spectra of (1) and (2). The cluster (3) exists as a mixture of three inseparable isomers which arise from the juxtaposition of the Ru atom around the three inequivalent positions of the metal 'butterfly'. The existence of these isomers is confirmed by a detailed analysis of the 1H and 31P n.m.r. spectra of this complex.
UR - http://www.scopus.com/inward/record.url?scp=37049069055&partnerID=8YFLogxK
U2 - 10.1039/DT9880001199
DO - 10.1039/DT9880001199
M3 - Article
AN - SCOPUS:37049069055
SN - 1472-7773
SP - 1199
EP - 1204
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 5
ER -