Advanced

Systematic Synthesis of Substituted Phosphido-bridged Osmium Clusters

Johnson, Brian F G; Lewis, Jack; Nordlander, Ebbe LU and Raithby, Paul R (1996) In Journal of the Chemical Society, Dalton Transactions p.755-763
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-PH2)], [Os6(µ-H)(CO)21(PMe3)(µ-PH2)], [Os6(µ-H)(CO)21(CNBut)(µ-PH2)], [Os6(µ-H)(CO)20{P(OMe)3}2(µ-PH 2)] and the corresponding phosphinidene-bridged clusters [Os6(µ-H)2-(CO)21 –nLn(µ3-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... (More)
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-PH2)], [Os6(µ-H)(CO)21(PMe3)(µ-PH2)], [Os6(µ-H)(CO)21(CNBut)(µ-PH2)], [Os6(µ-H)(CO)20{P(OMe)3}2(µ-PH 2)] and the corresponding phosphinidene-bridged clusters [Os6(µ-H)2-(CO)21 –nLn(µ3-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-PH 2)] 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. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the Chemical Society, Dalton Transactions
pages
755 - 763
publisher
Royal Society of Chemistry
ISSN
0300-9246
DOI
10.1039/DT9960000755
language
English
LU publication?
yes
id
b0053a20-ab87-4388-9d9c-258579c47da1 (old id 960986)
date added to LUP
2008-08-13 12:45:30
date last changed
2016-04-16 04:00:54
@article{b0053a20-ab87-4388-9d9c-258579c47da1,
  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-PH2)], [Os6(µ-H)(CO)21(PMe3)(µ-PH2)], [Os6(µ-H)(CO)21(CNBut)(µ-PH2)], [Os6(µ-H)(CO)20{P(OMe)3}2(µ-PH 2)] and the corresponding phosphinidene-bridged clusters [Os6(µ-H)2-(CO)21 –nLn(µ3-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-PH 2)] 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 Lewis, Jack and Nordlander, Ebbe and Raithby, Paul R},
  issn         = {0300-9246},
  language     = {eng},
  pages        = {755--763},
  publisher    = {Royal Society of Chemistry},
  series       = {Journal of the Chemical Society, Dalton Transactions},
  title        = {Systematic Synthesis of Substituted Phosphido-bridged Osmium Clusters},
  url          = {http://dx.doi.org/10.1039/DT9960000755},
  year         = {1996},
}