Abstract
The bonding in some platinum—gold cluster compounds has been analysed using semi-empirical molecular orbital calculations. In (PtAu 2(PR 3) 4Cl] + (I) and [Pt 2Au 2(PR 3) 4(CNR′) 4] 2+ (II) the platinum—gold bonding involves three-centre two-electron bonds between the bonding orbital of the Au 2(PR 3) 2 dimer and the frontier orbitals of the T-shaped platinum fragments. The observed distortions in II have been satisfactorily rationalised. In [Pt 3Au(μ-CO) 3(PR 3) 4] + (III) and [Pt 3Au(μ-SO 2) 2Cl(PR 3) 4] (IV) the AuPR 3 + fragments cap the Pt 3 triangles by utilising the acceptor orbital of a 1 symmetry localised on gold. The observed differences in bond lengths for these 54 and 56 electron clusters have been accounted for on the basis of the reduced overlap populations.
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