Elsevier

Polyhedron

Volume 3, Issue 2, 1984, Pages 199-212
Polyhedron

Closo clusters with unusual electron numbers: Localized bond schemes for n-atom clusters with n, (n + 1) or (n + 2) skeletal electron pairs

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Abstract

This paper considers whether satisfactory localized 2- and 3-centre bond schemes may be devized for real or hypothetical clusters BnHnc− (c = 0, 2 or 4; n = 4 → 12) or isoelectronic analogues thereof, with closo deltahedral shapes. As expected, localized bond schemes can be devized for all the species that would be predicted, using MO approaches, to have closed shell electronic configurations: these include species BnH2− (n = 5 → 12) and BnHnc− (c = 0 or 4; n = 4, 8, 9 or 11). There is also generally good agreement with MO treatments as to which systems are not expected to be stable: these include B4H42− and BnHnc− (c = 0 or 4; n = 5, 7 or 10). Localized bond treatments have value for estimating the bond orders of cluster bonds in species BnHn and BnHn2−, though they overestimate the bond orders in species BnHn4− (except when n = 4). They are misleading, when applied to octahedral and icosahedral systems, in indicating the former shape to be feasible for hypothetical species B6H6 and B6H64−, and the latter shape to be feasible for hypothetical species B12H12 and B12H124−.

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