The Influence of Nuclearity Upon the Reactivity of Metal Clusters
Jerome Keister Principal Investigator
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This project in the Inorganic, Bioinorganic and Organometallic Chemistry Program deals with the chemistry of metal cluster compounds, which are molecules containing three or more metal atoms joined together by metal-metal bonds. The physical and chemical properties of such clusters are different in many ways from those of compounds containing a single metal atom, and are useful models of metal surfaces or small metal particles, which are of technological importance as catalysts. The project will focus on the effects of nuclearity, i.e. the number of metal atoms, and of variations in the identity of the metal atoms of the cluster upon its chemical reactivity. The project will be divided into three areas of research, according to the size of the clusters. The chemistry of clusters containing three metal atoms bridged by a methylidyne ligand will be studied, with the goal of understanding the electrochemically-induced chemistry of the methylidyne ligand and the influence of the identities of the metal atoms (Fe, Ru or Os). The chemistry of clusters containing four metal atoms, of which three or four are bridged by methylidyne ligands, will be studied with the goal of comparing the chemical reactivity of the methylidyne ligand on clusters of three or four metal atoms. The chemical and electrochemical behavior of large clusters of nine to eighteen rhodium atoms will be studied to determine how these properties are influenced by the nuclearity, charge and face geometries of the cluster. The ultimate goal of the work is to determine the way in which the properties of metal clusters differ from small metal particles and from monometallic metal complexes and to be able to selectively modify these properties by changing the number and identities of the metal atons and the coordination sphere of the cluster.