Electronic Symmetry and Dissymmetry in Catalysis

Seth Brown教授是圣母大学化学和生物化学系的一名教员，他得到了无机化学、生物无机化学和金属有机化学项目的支持，以测试关于过渡金属催化剂设计的两个假设。第一个假设是，在需要两位底物结合的催化反应中，反式效应可以影响过渡态能量与底物施主性质的匹配。第二个假设是电子不对称，即手性键模式，可以区分不同的对映体，因此手性立体因子不是非对映选择性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)络合物将被用来探索这些假说。催化在化学工业中对于节能和控制立体化学的重要性确保了提高我们对催化循环机理的理解的影响。该项目提供了对早期过渡金属有机金属络合物的化学原理特征的洞察，将指导未来的催化剂设计。

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.