Bimetallic Cooperativity in Homogeneous Catalysis

均相催化中的双金属协同作用

• 批准号: 9700526
• 负责人: George Stanley
• 金额: $ 34.65万
• 依托单位: Louisiana State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-05-01 至 2000-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9700526&HistoricalAwards=false
• 关键词: Bimetallic; Cooperativity; Homogeneous; Catalysis

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program continues support for research on homogeneous catalysis by Dr. George G. Stanley of the Chemistry Department, Louisiana State University. The goal of the work is to understand cooperativity in bimetallic catalysis by studying a dirhodium complex that is active and selective in hydroformylation. This dicationic complex contains a binucleating tetraphosphine ligand. The nature of the binding site will be elucidated with the aid of molecular modeling, in addition to experimental approaches, including kinetic, spectroscopic and isotopic labeling studies. The results will be used to make improvements in the regio- and enantioselectivty of the catalyst. After this stage of the research, attempts will be made to extend bimetallic cooperativity to other catalytic reactions, such as hydrosilylation, silylformylation, hydrocyanation, and C-C bond coupling reactions with alkenes and alkynes. In some catalytic systems, the cooperative action of two different metal sites has been suggested to be effective in promoting reactions not only more quickly, but also shape-specifically. In this project, the potential of cooperativity in catalyst design will be determined. The ability to control reaction rates and products is very important in many areas of chemical manufacturing, such as production of pharmaceuticals, polymers, and fine chemicals.

这个无机、生物无机和有机金属化学项目的奖项继续支持路易斯安那州立大学化学系的George G. Stanley博士对均相催化的研究。这项工作的目的是通过研究一种在氢甲酰化中具有活性和选择性的镝配合物来了解双金属催化中的协同性。这个配体包含一个双核的四膦配体。结合位点的性质将在分子模型的帮助下得到阐明，除了实验方法，包括动力学、光谱和同位素标记研究。研究结果将用于改进催化剂的区域选择性和对映选择性。在这一阶段的研究之后，将尝试将双金属的协同性扩展到其他催化反应中，如硅氢化、硅甲酰基化、氢氰化以及与烯烃和炔的C-C键偶联反应。在一些催化体系中，两种不同金属位点的协同作用被认为不仅可以更快地促进反应，而且可以特异性地促进反应。在这个项目中，协同作用在催化剂设计中的潜力将被确定。控制反应速率和产物的能力在化学制造的许多领域非常重要，例如药品、聚合物和精细化学品的生产。