Transition-metal clusters: geometric and electronic structure

Abstract

To a large extent, we expect the cluster bonding principles established for main-group clusters in Chapter 2 to carry over to transition-metal clusters. However, the AO basis sets for building MOs differ for transition metals which means that the expression of the cluster bonding principles in geometric and electronic structure will also differ. That is, the observed cluster compositions and shapes differ and these differences can be associated with the participation of the metal d functions in cluster bonding. The d functions are the “wild cards” that make transition-metal chemistry so interestingly different from main-group chemistry. In writing Chapter 3 we have assumed that the reader has a basic understanding of the principles of cluster bonding as expressed by p-block clusters (Chapter 2). Emphasis here is placed on the varied expression of d-block metal character within a cluster context. A number of monographs on metal clusters are suggested at the end of this chapter as additional reading for those interested in pursuing a topic in more depth.