Electronic Symmetry and Dissymmetry in Catalysis

催化中的电子对称性和不对称性

• 批准号: 0518243
• 负责人: Seth Brown
• 金额: $ 36.6万
• 依托单位: University of Notre Dame
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-09-01 至 2009-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0518243&HistoricalAwards=false
• 关键词: Electronic; Symmetry; Dissymmetry; Catalysis

Professor Seth Brown, a faculty member in the Department of Chemistry and Biochemistry at the University of Notre Dame, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program to test two hypotheses concerning transition metal catalyst design. The first hypothesis is that the trans effect can be influential in matching transition state energies with substrate donor properties in catalytic reactions requiring two-site substrate binding. The second hypothesis is that electronic dissymmetry, that is a chiral bonding pattern, can discriminate between enantiomers, so chiral steric factors are not a prerequisite for diastereoselective reaction control. Octahedral titanium(IV) complexes bound to beta-diketonate ligand derivatives will be used to probe these hypotheses.The importance of catalysis in the chemical industry both for conserving energy and for controlling stereochemistry insures the impact of improving our mechanistic understanding of catalytic cycles. This project provides insight into chemical principles characteristic of early transition metal organometallic complexes that will guide future catalyst design.

巴黎圣母院化学和生物化学系的教职员工塞思·布朗（Seth Brown）教授得到了无机，生物无机和有机金属化学计划的支持，以测试有关过渡金属催化剂设计的两个假设。 第一个假设是，反式效应在需要两个位点底物结合的催化反应中，在匹配过渡状态与底物供体特性的匹配中可能具有影响力。 第二个假设是电子键合的电子键合模式可以区分对映异构体，因此手性空间因子不是对映射反应控制的先决条件。与β-二酮配体衍生物结合的八面体钛（IV）复合物将用于探测这些假设。化学工业中催化的重要性既可以保存能量和控制立体化学，从而确保了我们对催化周期的机械理解的影响。 该项目可深入了解早期过渡金属有机金属络合物的特征，这些复合物将指导未来的催化剂设计。