New supraicosahedral metallacarboranes. The synthesis and molecular structures of 4-dppe-4,1,6-closo-NiC2B10H12 and [4-(η-C3H5)-4-(CO)2-4,1,6-closo-MoC 2B10H12]-

Miguel A. Laguna, David Ellis, Georgina M. Rosair, Alan J. Welch

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

The new 13-vertex nickelacarborane 4-dppe-4,1,6-closo-NiC2B10H12 and molybdacarborane [4-(?-C3H5)-4-(CO)2-4,1,6-closo-MoC 2B10H12]- have been prepared. The structure of the CH2Cl2 solvate of the nickel species has been studied as two crystalline modifications. The molybdacarborane was also studied crystallographically as its [PhCH2NMe3]+ salt. The differing trans influences of C and B atoms in the metalla-bonded C2B4 carborane ligand face are used to rationalise the difference in Ni-P distances in the nickelacarborane and the orientation of the {Mo(C3H5)(CO)2} fragment in the molybdacarborane. Both metallacarboranes display fluxionality in solution at room temperature which can be arrested by cooling. An activation energy for the presumed double diamond-square-diamond fluxional process is calculated to be ca. 47 kJ mol-1 by analysis of the 1H and 31P NMR spectra of the nickelacarborane. For the molybdacarborane the equivalent activation energy is ca. 40 kJ mol-1 from the 1H spectrum. © 2002 Elsevier Science B.V. All rights reserved.

Original languageEnglish
Pages (from-to)161-167
Number of pages7
JournalInorganica Chimica Acta
Volume347
DOIs
Publication statusPublished - 15 Apr 2003

Keywords

  • Crystallography
  • Fluxionality
  • Metallacarborane
  • NMR spectroscopy
  • Synthesis

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