Theoretical aspects of metal cluster chemistry

Abstract

During the last twenty years the Polyhedral Skeletal Electron Pair Theory and the isolobal analogy have provided a theoretical basis for the rapid experimental developments, which have occurred in metal cluster chemistry. These theoretical principles have been underpinned by m.o. calculations on specific molecules and more generally by the Tensor Surface Harmonic Theory. This paper will review the important theoretical developments and relate them to the experimental and structural data which have been obtained for cluster compounds in our own and other laboratories. In particular the application of theoretical principles for rationalising and predicting the structures of cluster compounds of the platinum metals and gold are discussed. The bonding requirements of interstitial atoms and fragments are discussed, particularly in the contextof interstitial C, B, N and transition metal atoms and diatomic fragments, e.g. C2 and C-H. © 1991 IUPAC