Reactivity and Catalysis at Sulfur-Rich Metal Centers

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This award in the Inorganic, Bioinorganic, and Organometallic Chemistry program supports research on inorganic sulfido complexes by Dr. Thomas B. Rauchfuss of the Chemistry Department, University of Illinois. The thioanion ReS4- has been found to react with alkenes, alkynes and nitriles. This chemistry will be investigated further and extended to include other substrates, atom- and group transfers, mechanism, and applications to organic synthesis and cluster and solid state chemistry. Of particular interest will be investigation of the binding of unsaturated organic substrates to S=M=S in the presence of H2S, thus mimicking the reaction conditions found in HDS catalysis. Odd-electron metal sulfides, electropolymerization routes to novel sulfur-rich solids, and the generation of reduced metal sulfides capable of binding to HDS-relevant substrates will be investigated. Studies of the catalytic properties of ReS4- will focus on the mechanism of H2 activation, routes to 1,2-dithiols, and the ability to bind nitriles and isonitriles through sulfur.Hydrodesulfurization (HDS) is a large scale industrial process to remove sulfur from petroleum. The process is catalyzed by metal-based compounds, often containing MoS2. Strong C-S and H-H bonds are activated in the presence of H2S. The design of future catalysts that will effectively and efficiently remove sulfur from deteriorating fossil fuel reserves depends on better fundamental understanding of the structural and electronic features that confer high reactivity on the MSx species generated during the catalytic process. Metal sulfides that affect many HDS-relevant reactions will be studied by this research group, which includes undergraduate and graduate students.