Metal clusters on supports: synthesis, structure, reactivity, and catalytic properties.

This review of structurally simple and essentially molecular metal clusters on solid supports addresses synthesis, characterization, reactivity, and catalysis. Examples of supported clusters made in high yields are Os(3), Ir(4), Ir(6), and Rh(6), and typical supports are MgO, gamma-Al(2)O(3), and zeolites. Supported clusters are synthesized by adsorption of ligated molecular metal clusters, deposition of bare size-selected metal clusters from the gas phase, and adsorption of metal complexes followed by treatment to form clusters. Some metal clusters on supports have been imaged with atomic resolution. Reactions of supported metal clusters include ligand modifications, oxidative fragmentation, and migration leading to aggregation. Reactivities and catalytic properties of the clusters (e.g., for alkene hydrogenation and epoxidation) depend on the cluster size and the support (which acts as a ligand) and are distinct from those of supported particles that resemble bulk metals. Opportunities for deeper understanding of the chemistry of supported metal clusters hinge on improvements in characterization techniques such as X-ray absorption spectroscopy and high-resolution transmission electron microscopy.