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Issue 13, 2014
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Asymmetric 1,8/13,2,x-M2C2B10 14-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions§

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Abstract

The isolation of six isomeric, low-symmetry, dicobaltacarboranes with bicapped hexagonal antiprismatic cage structures, always in low yield, is described from reactions in which 13-vertex cobaltacarborane anions and sources of cobalt-containing cations were present. The vertex-to-centroid distance (VCD) and boron–H distance (BHD) methods are used to locate the correct C atom positions in the cages, thus allowing the compounds to be identified as 1,13-Cp2-1,13,2,10-closo-Co2C2B10H12 (1), 1,8-Cp2-3-OEt-1,8,2,10-closo-Co2C2B10H11 (2), 1,13-Cp2-1,13,2,9-closo-Co2C2B10H12 (3), 1,8-Cp2-1,8,2,4-closo-Co2C2B10H12 (4), 1,13-Cp2-1,13,2,4-closo-Co2C2B10H12 (5) and 1,8-Cp2-1,8,2,5-closo-Co2C2B10H12 (6). It is shown that a common alternative method of cage C atom identification, using refined (as B) Ueq values, does not work well, at least in these cases. Having identified the correct isomeric forms of the six dicobaltacarboranes, their syntheses are tentatively rationalised in terms of the direct electrophilic insertion of a {CpCo+} fragment into [CpCoC2B10] anions and it is demonstrated that compounds 1, 4, 5 and 6 can be successfully prepared by deliberately performing such reactions.

Graphical abstract: Asymmetric 1,8/13,2,x-M2C2B10 14-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions

  • This article is part of the themed collection: Carboranes
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Supplementary files

Article information


Submitted
02 Aug 2013
Accepted
07 Oct 2013
First published
08 Oct 2013

This article is Open Access

Dalton Trans., 2014,43, 5095-5105
Article type
Paper

Asymmetric 1,8/13,2,x-M2C2B10 14-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions

A. McAnaw, M. E. Lopez, D. Ellis, G. M. Rosair and A. J. Welch, Dalton Trans., 2014, 43, 5095
DOI: 10.1039/C3DT52101J

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