Systematic synthesis of substituted hexanuclear phosphide- and phosphinidene-bridged osmium clusters

Brian F.G. Johnson; Jack Lewis; Ebbe Nordlander; Paul R. Raithby

doi:10.1039/dt9960000755

Systematic synthesis of substituted hexanuclear phosphide- and phosphinidene-bridged osmium clusters

Brian F.G. Johnson, Jack Lewis, Ebbe Nordlander, Paul R. Raithby

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Abstract

The labilised clusters [Os₃(CO)_11-nL_n(NCMe)] [n = 1, L = PMe₃ or CNBu^t; n = 2, L = P(OMe)₃] have been prepared. The reaction of [Os₃(CO)_11-nL_n(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(CNBu^t)(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-nL_n(μ ₃-PH)] [n = 1, L = CNBu^t; 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.

Original language	English
Pages (from-to)	755-763
Number of pages	9
Journal	Journal of the Chemical Society - Dalton Transactions
Volume	1996
Issue number	5
DOIs	https://doi.org/10.1039/dt9960000755
Publication status	Published - 7 Mar 1996

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General Chemistry

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10.1039/dt9960000755

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@article{ce4465e259cf470fa06997cc92b66b84,

title = "Systematic synthesis of substituted hexanuclear phosphide- and phosphinidene-bridged osmium clusters",

abstract = "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.",

author = "Johnson, \{Brian F.G.\} and Jack Lewis and Ebbe Nordlander and Raithby, \{Paul R.\}",

year = "1996",

month = mar,

day = "7",

doi = "10.1039/dt9960000755",

language = "English",

volume = "1996",

pages = "755--763",

journal = "Journal of the Chemical Society - Dalton Transactions",

issn = "0300-9246",

publisher = "Royal Society of Chemistry",

number = "5",

}

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 - https://www.scopus.com/pages/publications/33748445945

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 -

Systematic synthesis of substituted hexanuclear phosphide- and phosphinidene-bridged osmium clusters

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