Reactivity and Catalysis at Sulfur-Rich Metal Centers

富硫金属中心的反应性和催化

• 批准号: 9981979
• 负责人: Thomas Rauchfuss
• 金额: $ 40.4万
• 依托单位: University of Illinois at Urbana-Champaign
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-02-15 至 2005-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9981979&HistoricalAwards=false
• 关键词: Reactivity; Catalysis; Sulfur; Rich; Metal

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.

该奖项属于无机、生物无机和有机金属化学项目，用于支持伊利诺伊大学化学系 Thomas B. Rauchfuss 博士对无机硫化物配合物的研究。 硫阴离子 ReS4- 已被发现能与烯烃、炔烃和腈发生反应。 该化学将得到进一步研究并扩展到包括其他底物、原子和基团转移、机制以及在有机合成、簇和固态化学中的应用。 特别感兴趣的是研究在 H2S 存在下不饱和有机底物与 S=M=S 的结合，从而模拟 HDS 催化中的反应条件。 将研究奇电子金属硫化物、新型富硫固体的电聚合途径，以及能够与 HDS 相关底物结合的还原金属硫化物的生成。 ReS4- 催化性能的研究将集中于 H2 活化机制、生成 1,2-二硫醇的途径以及通过硫结合腈和异腈的能力。加氢脱硫 (HDS) 是一种从石油中脱除硫的大规模工业过程。 该过程由通常含有 MoS2 的金属化合物催化。强 C-S 和 H-H 键在 H2S 存在下被激活。 未来催化剂的设计能否有效地从日益恶化的化石燃料储量中去除硫，取决于对催化过程中产生的 MSx 物质具有高反应性的结构和电子特征的更好的基本了解。 该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。