Novel Inorganic Ligand Architectures for Catalysis

用于催化的新型无机配体结构

• 批准号: 0317089
• 负责人: Thedford Hollis
• 金额: $ 37.5万
• 依托单位: University of California-Riverside
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-08-01 至 2007-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0317089&HistoricalAwards=false
• 关键词: Novel; Inorganic; Ligand; Architectures; Catalysis

T. Keith Hollis, University of California-Riverside, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program for studies of phosphametallocene catalysts. These compounds have one or two phosphacyclopentadienyl ligands coordinated to a transition metal. The phosphorus in the aromatic ring gives rise to unique isomerization pathways, including ring slip and P-inversion. These processes have stereochemical consequences and can lead to the dynamic resolution of metallocenes, chiral catalysts and oscillating catalysts. Extensions to other heterometallocene systems such as boratabenzene, pyrrolyl and arsolyl may lead to similar isomerizations and yield additional useful chiral catalysts.Chiral metallocene catalysts have been applied in several processes, including olefin polymerization, epoxide ring opening, asymmetric hydrogenation, asymmetric allylic alkylation and enantioselective isomerization of allylic alcohols. The heterometallocenes developed in this project offer new potential catalysts for many transformations of interest to pharmaceutical and fine chemical producers. Students working on this project will be trained in organometallic and organic chemistry, including parallel combinatorial chemistry, and in polymer chemistry.

T. Keith Hollis，加州大学河滨分校，由无机、生物无机和有机金属化学项目资助，研究磷茂金属催化剂。这些化合物具有一个或两个与过渡金属配位的磷酸环戊二烯基配体。芳香环上的磷产生了独特的异构化途径，包括环滑移和p反转。这些过程具有立体化学的影响，可以导致茂金属、手性催化剂和振荡催化剂的动态分解。延伸到其他异金属体系，如硼二苯、吡啶和芳索基，可能导致类似的异构化，并产生额外的有用的手性催化剂。手性茂金属催化剂已应用于烯烃聚合、环氧化物开环、不对称加氢、不对称烯丙基烷基化和烯丙醇对映选择性异构化等过程。在这个项目中开发的异金属二茂物为制药和精细化工生产商感兴趣的许多转化提供了新的潜在催化剂。参与该项目的学生将接受有机金属和有机化学，包括平行组合化学和聚合物化学方面的培训。