Discrete and Extended Arrays of Main Group Elements and Transition Metals

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With this award, the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research by Kenton H. Whitmire, Department of Chemistry, Rice University, on clusters of main group elements (E) and transition metals (M). New techniques will be used to synthesize large, novel E-M cluster compounds with new bonding and reactivity characteristics. Heavy p-block elements often form unusual compounds because of their size, Lewis acid-base properties, metallic character and relativistic effects. The high-pressure synthesis will be monitored by infrared spectroscopy in a specially designed cell. The bonding will be analyzed in collaboration with Dr. Jean-Yves Saillard of the Universite de Rennes, France. The compounds will be characterized using x-ray diffraction, NMR and IR spectroscopies, and magnetic susceptibility. In addition, the catalytic activity of the M3E family of cluster compounds will be studied by in situ analysis of the kinetics and mechanism of carbonylation and hydrogenation reactions. The role of the main group element is of particular interest. The high-pressure reactor used in the synthetic studies will be used in this investigation to monitor the effects of cluster composition, reactant gas pressure, and solvent and ion pairing on cluster stability.The interaction of main group elements and transition metals is important in chemistry, materials science and catalysis. Alloys containing elements of the p- and d- blocks have interesting electronic and magnetic properties. Understanding how these different elements form structures, bond, and react is important in characterizing discrete compounds and also in extended solid state phases. For the first time, both formation of these elements into large clusters and their behavior in catalytic reactions will be studied in detail in real time. Graduate and undergraduate students would learn how to integrate experimental and theoretical results.