Structure and bonding patterns in large molecular ligated metal clusters

Abstract

Although there will always be an Edisonian component to a search for new cluster compounds, the greater the understanding of the underlying chemistry, the more focused and efficient the search. It is why the rapid expansion of the synthesis and characterization of ligated transition-metal clusters over the last decades has been accompanied by theories about their bonding and electronic properties with the aid of conceptual ideas and theoretical models such as the development of electron-counting rules which govern the relationship between the structure and the electron count. This review summarizes these theoretical models, their historical development, their limits, and using a selection of specific examples among the extensive panoply of large ligated metal clusters available in the literature, shows how they can help in understanding their structural and electronic properties.