Abstract
Extended-Hückel molecular-orbital calculations are reported for the icosahedrel platinaboranes and carbaboranes [B11{Pt(PH3)2}H11]2–, [B10C{Pt(PH3)2}H11], and B9C2[Pt(PH3)2]H11. The failure of the polyhedral skeletal electron-counting rules when applied to carbaplatinaboranes is discussed, and attributed to the unequal bonding capabilities of the platinum 5dxz and 5dyz orbitals in the Pt(PH3)2 fragment. The conformations of icosahedral carbaplatinaboranes are rationalised on the basis of the symmetry characteristics of the lowest-unoccupied orbital of thecarbaboraneand the highest-occupied orbital ofthe metal-phosphine moiety. Analogous d8 metal compounds are predicted to be stable and expected to have conformations which are complementary to those observed for d10 metal compounds.

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