In:
Pure and Applied Chemistry, Walter de Gruyter GmbH, Vol. 75, No. 9 ( 2003-01-01), p. 1325-1333
Abstract:
Although supraicosahedral (hetero) boranes have long been of interest to theoreticians, the area is under-developed from a synthetic viewpoint. The synthesis of supraicosahedral carboranes by reduction then capitation ( RedCap ) of C 2 B 10 species is attractive, but unsuccessful as long as the cage carbon atoms are free to separate in the reduction step. Studies on 4,1,6-MC 2 B 10 13-vertex metallacarboranes have shown that the partial degradation of such species can be a facile process, in spite of the fact that the binding energy of the metal atom to the carborane framework can be at least as high as that of a {BH}fragment. These findings support the general concept of the kinetic instability of 1,6-C 2 B 11 species, explaining why a supraicosahedral carborane could not be made from 1,2-C 2 B 10 H 12 . However, tethering together the two cage C atoms with a C 6 H 4 (CH 2 ) 2 strap ultimately allowed the synthesis of the first supraicosahedral carborane. This species has a henicosahedral geometry, and there is evidence that a facile rearrangement from kinetic to thermodynamic isomer has occurred. The RedCap synthesis of this unprecedented cluster has the potential to be applied successively, yielding 14-,15-,16-, etc. vertex carboranes, the larger of which may be sufficiently kinetically stable to exist without a C,C tether.
Type of Medium:
Online Resource
ISSN:
1365-3075
,
0033-4545
DOI:
10.1351/pac200375091325
Language:
English
Publisher:
Walter de Gruyter GmbH
Publication Date:
2003
detail.hit.zdb_id:
2022101-0
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