TY - JOUR
T1 - Systematic synthesis of substituted hexanuclear phosphide- and phosphinidene-bridged osmium clusters
AU - Johnson, Brian F.G.
AU - Lewis, Jack
AU - Nordlander, Ebbe
AU - Raithby, Paul R.
PY - 1996/3/7
Y1 - 1996/3/7
N2 - The labilised clusters [Os3(CO)11-nLn(NCMe)] [n = 1, L = PMe3 or CNBut; n = 2, L = P(OMe)3] have been prepared. The reaction of [Os3(CO)11-nLn(NCMe)] or [Os3(CO)10{P(OMe)3}(NCMe)] with either [Os3(CO)11(PH3)] or [Os3(μ-H)(CO)10(μ-PH2)] led to the formation of the phosphide-bridged clusters [Os6(μ-H)(CO)21{P(OMe)3}(μ-PH 2)], [Os6(μ-H)(CO)21(PMe3)(μ-PH2)] , [Os6(μ-H)(CO)21(CNBut)(μ-PH 2)], [Os6(μ-H)(CO)20{P(OMe)3} 2(μ-PH2)] and the corresponding phosphinidene-bridged clusters [Os6(μ-H)2-(CO)21-nLn(μ 3-PH)] [n = 1, L = CNBut; n = 2, L = P(OMe)3] in good yield. The Os6 clusters have been fully characterised on the basis of their spectroscopic data and the molecular structures of three have been established by single-crystal X-ray analysis. The structures of [Os6(μ-H)(CO)20{P(OMe)3} 2(μ-PH2)] and [Os6(μ-H)2(CO)19{P(OMe)3} 2(μ3-PH)] differ from those of previously studied hexanuclear phosphide- and phosphinidene-bridged clusters; this difference is attributed to the steric influence of the relatively bulky phosphite ligands. Proton and phosphorus NMR spectroscopy indicate that both these clusters exist in two isomeric forms in solution.
AB - The labilised clusters [Os3(CO)11-nLn(NCMe)] [n = 1, L = PMe3 or CNBut; n = 2, L = P(OMe)3] have been prepared. The reaction of [Os3(CO)11-nLn(NCMe)] or [Os3(CO)10{P(OMe)3}(NCMe)] with either [Os3(CO)11(PH3)] or [Os3(μ-H)(CO)10(μ-PH2)] led to the formation of the phosphide-bridged clusters [Os6(μ-H)(CO)21{P(OMe)3}(μ-PH 2)], [Os6(μ-H)(CO)21(PMe3)(μ-PH2)] , [Os6(μ-H)(CO)21(CNBut)(μ-PH 2)], [Os6(μ-H)(CO)20{P(OMe)3} 2(μ-PH2)] and the corresponding phosphinidene-bridged clusters [Os6(μ-H)2-(CO)21-nLn(μ 3-PH)] [n = 1, L = CNBut; n = 2, L = P(OMe)3] in good yield. The Os6 clusters have been fully characterised on the basis of their spectroscopic data and the molecular structures of three have been established by single-crystal X-ray analysis. The structures of [Os6(μ-H)(CO)20{P(OMe)3} 2(μ-PH2)] and [Os6(μ-H)2(CO)19{P(OMe)3} 2(μ3-PH)] differ from those of previously studied hexanuclear phosphide- and phosphinidene-bridged clusters; this difference is attributed to the steric influence of the relatively bulky phosphite ligands. Proton and phosphorus NMR spectroscopy indicate that both these clusters exist in two isomeric forms in solution.
UR - http://www.scopus.com/inward/record.url?scp=33748445945&partnerID=8YFLogxK
U2 - 10.1039/dt9960000755
DO - 10.1039/dt9960000755
M3 - Article
AN - SCOPUS:33748445945
SN - 0300-9246
VL - 1996
SP - 755
EP - 763
JO - Journal of the Chemical Society - Dalton Transactions
JF - Journal of the Chemical Society - Dalton Transactions
IS - 5
ER -