Electrochemical and Synthetic Studies of Organometallics

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With this award, the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research on organometallic radicals by Dr. Dwight A. Sweigart of the Chemistry Department, Brown University. Ligand substitution reactions, metal dependence of reactivity patterns, and rates of electron transfer reactions will be investigated for electrochemically generated 17- or 19- electron species. In addition, catalytic ligand substitution and electroactivation of hydrocarbons will be studied. A second area of investigation is metal-promoted synthetic routes to indoles, diterpenes, and steroids. Chiral metal complexes will be tested as effective reagents in the preparation of optically pure products. High oxidation state species are expected in the reaction of oxirenes with metals to form the first oxirene-metal complexes. Odd-electron organometallic compounds are reactive species thought to play important roles in catalytic reactions. Using electrochemical methods, Sweigart can produce and characterize these species directly and thus predict their reactivities. Because the systems to be studied include both homogeneous and heterogenous examples, the results will provide insight into surface corrosion as well as solution reactions. The investigation of large hydrocarbon ring compounds is biologically relevant and establishing controlled synthetic routes may prove useful to many investigators. The study will also extend the electrochemical methods available for characterizing chemical processes.