Towards the mechanism of heteroborane isomerisation: 1,2 → 1,2 and 1,2 → 1,7 low-temperature isomerisations from metallations of [5-I-7,8-Ph 2-7,8-nido-C2B9H8]2-

Susan Robertson, Rhona M. Garrioch, David Ellis, Thomas D. McGrath, Bruce E. Hodson, Georgina M. Rosair, Alan J. Welch

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The reaction between [5-I-7,8-Ph2-7,8-nido-C2B 9H8]2- and NiCl2(dppe) affords 1,2-Ph2-4,4-dppe-12-I-4,1,2-closo-NiC2B9H 8 (1) and 1,8-Ph2-2,2-dppe-10-I-2,1,8-closo-NiC 2B9H8 (2). Reaction between the same carborane ligand and cis-PtCl2(PMe2Ph)2 yields three species, 1,8-Ph2-2,2-(PMe2Ph)2-10-I-2,1,8- closo-PtC2B9H8 (3), 1,8-Ph2-2,2- (PMe2Ph)2-12-I-2,1,8-closo-PtC2B 9H8 (4), and 1,8-Ph2-2,2-(PMe 2Ph)2-7-I-2,1,8-closo-PtC2B9H 8 (5). Compounds 1-5 have been characterised spectroscopically and crystallographically. The 4,1,2-MC2B9 architecture of 1 constitutes a "1,2 ? 1,2" cage C atom isomerisation, and the 2,1,8-MC2B9 architectures of 2-5 a 1,2 ? 1,7 cage C atom isomerisation, relative to the presumed first product of the metallations, 1,2-Ph2-3,3-L2-9-I-3,1,2-closo-MC2B 9H8 [M = Ni, L2 = dppe; M = Pt, L2 = (PMe2Ph)2]. The location of the (iodide) labelled boron vertex in the products allows speculation as to the mechanism of these isomerisations and the possible involvement of triangle face rotation is discussed. © 2004 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)1485-1493
Number of pages9
JournalInorganica Chimica Acta
Volume358
Issue number5 SPEC. ISS.
DOIs
Publication statusPublished - 15 Mar 2005

Keywords

  • Isomerisation mechanisms
  • Metallacarborane
  • NMR spectroscopy
  • Synthesis
  • Vertex labelling
  • X-ray crystallography

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