Reactivity and Catalysis at Sulfur-Rich Metal Centers

无机，生物无机和有机化学计划的这一奖项支持了托马斯B博士对无机硫化物复合物的研究。伊利诺斯大学化学系的劳赫福斯说。 硫代阴离子ReS ~（4-）可与烯烃、炔和腈反应。 这种化学将进一步研究和扩展到包括其他基板，原子和基团的转移，机制，并应用于有机合成和集群和固态化学。 特别感兴趣的将是调查的结合不饱和有机底物S=M=S在硫化氢的存在下，从而模仿HDS催化中发现的反应条件。 奇电子金属硫化物，电聚合路线，以新颖的富硫固体，并产生还原金属硫化物能够绑定到HDS相关的基板将进行研究。 ReS_（4-）催化剂的研究主要集中在其活化氢的机理、生成1，2-二硫醇的途径以及通过硫与腈和异腈结合的能力等方面。加氢脱硫（HDS）是一种大规模工业化的石油脱硫工艺。 该过程由金属基化合物催化，通常含有MoS 2。强C-S和H-H键在H2S存在下活化。 未来催化剂的设计，将有效和高效地从日益恶化的化石燃料储备中去除硫，取决于对催化过程中产生的MSx物质的高反应性的结构和电子特征的更好的基本理解。 这个研究小组将研究影响许多HDS相关反应的金属硫化物，该研究小组包括本科生和研究生。

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.