Reactivity and Catalysis at Sulfur-Rich Metal Centers

伊利诺伊大学化学系的Thomas B.Ruchfuss博士在无机、生物无机化学和金属有机化学项目中获得该奖项，以支持其对无机硫化物的研究。硫代阴离子ReS4-已被发现与烯烃、炔烃和腈反应。这一化学将被进一步研究并扩展到包括其他底物、原子和基团转移、机理以及在有机合成、团簇和固态化学中的应用。特别令人感兴趣的是研究不饱和有机底物在硫化氢存在下与S=M=S的结合，从而模拟加氢脱硫催化中的反应条件。将研究奇电子金属硫化物、电聚合途径获得新型富硫固体，以及能够与HDS相关底物结合的还原金属硫化物的生成。对ReS4-催化性能的研究将集中在氢活化机理、生成1，2-二硫醇的途径以及通过硫磺结合氰化物和异腈的能力。加氢脱硫(HDS)是一种从石油中脱除硫的大规模工业过程。这个过程是由金属基化合物催化的，通常含有MoS2。在H_2S存在下，强C-S键和H-H键被激活。未来催化剂的设计将有效和高效地从不断恶化的化石燃料储备中脱除硫，这取决于对催化过程中产生的MSX物种具有高反应性的结构和电子特征的更好的基本了解。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.