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Ebbe Nordlander. Portrait.

Ebbe Nordlander

Professor

Ebbe Nordlander. Portrait.

Synthesis, characterisation and natural abundance Os-187 NMR spectroscopy of hydride bridged triosmium clusters with chiral diphosphine ligands

Author

  • MJ Stchedroff
  • Viktor Moberg
  • Eduardo Rodriguez
  • AE Aliev
  • J Bottcher
  • JW Steed
  • Ebbe Nordlander
  • M Monari
  • AJ Deeming

Summary, in English

Treatment of [Os-3(mu-H)(2)(CO)(10)] with the chiral diphosphines BINAP, tolBINAP [(R)-2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl], DIOP [(4R,5R)-(-)-O-isopropenylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino) butane] affords [Os-3(mu-H)(2)(CO)(8)(mu-L)] (L = BINAP (1), tolBINAP (2), DIOP (4)) in high yield. The X-ray structures for 1, 2 and 4 are reported, and structural and spectroscopic comparisons are made between these clusters and [Os-3(mu-H)(2)(CO)(8)(mu-L)] (L = dppm (5), dppe (6), dppp (7)) which were synthesised similarly. Compounds 5 to 7 were previously synthesised by hydrogenation of 1,2-[OS3(CO)(10)(mu-L)] but the route from [Os(mu-H)(2)(CO)(10)] is preferable. The H-bridged Os center dot center dot Os distances are similar in 1, 2 and 4 indicating that these species are formally unsaturated 46-electron clusters. The P center dot center dot center dot P distances vary from 4.24 to 4.30 angstrom in 1 and 2, respectively, to 4.53 angstrom in 4 and there are related changes in the angles associated with the ligand set around the H-bridged osmium atoms. Introduction of the diphosphine ligands completely suppresses the ability to add CO, to insert acetylene to form a mu-eta(1), eta(2)-vinyl compound, and to exchange hydride ligands with styrene-d(8), which are reactions characteristic of [Os-3(mu-H)(2)(CO)(10)], Clusters 2 and 5-7 were also used to examine the potential of natural abundance Os-187 NMR spectroscopy through techniques based on inverse detection by HMQC, HSQC and HMBC spectroscopy. (c) 2005 Elsevier B.V. All rights reserved.

Department/s

  • Chemical Physics
  • Centre for Analysis and Synthesis

Publishing year

2006

Language

English

Pages

926-937

Publication/Series

Inorganica Chimica Acta

Volume

359

Issue

3

Document type

Journal article

Publisher

Elsevier

Topic

  • Analytical Chemistry
  • Atom and Molecular Physics and Optics

Keywords

  • NMR
  • chiral phosphine
  • osmium
  • cluster

Status

Published

ISBN/ISSN/Other

  • ISSN: 0020-1693