Kinetics and Mechanisms of Organometallic Reactions

在这项由无机化学、生物无机化学和金属有机化学项目支持的研究中，伊利诺伊大学香槟分校的西奥多·L·布朗将研究有机金属反应的动力学和机理。重点将主要放在过渡金属羰基络合物上，特别是在有机金属反应过程中形成的反应中间体的性质上。这些研究对于了解有机金属化学和涉及有机金属化合物的催化过程具有重要意义。一类需要研究的反应中间体是金属羰基，它在金属价轨道上具有奇数个电子(通常是17个或19个)。第二类中间体是通过失去与金属结合的配体而形成的，通常是一氧化碳。使用氮气激光的闪光光解技术将被用来研究这些中间体。这项研究的另一个方面将涉及对配体，主要是磷配体的空间和电子性质的全面研究。该方法将包括对适当的一系列反应进行实验研究；汇编这些结果和大量现有文献的结果；以及使用新的统计有效方法分析这些数据。最终的结果可能是一个有用的系统，通过使用赋予催化剂可预测和期望的性质的配体来有效地设计催化剂。

In this research supported in the Inorganic, Bioinorganic and Organometallic Chemistry Program, Theodore L. Brown of the University of Illinois at Urbana-Champaign, will investigate the kinetics and mechanisms of organometallic reactions. The focus will be mainly on transition-metal carbonyl complexes and specifically on the properties of reaction intermediates formed in the course of organometallic reactions. These studies are important for the fundamental understanding of organo- metallic chemistry and catalytic processes involving organo- metallic compounds. One class of reaction intermediate to be studied is the metal carbonyl radicals, which possess an odd number of electrons (often seventeen or nineteen) in the metal valence orbitals. A second class of intermediate is formed by loss of a ligand, usually carbon monoxide, bound to the metal. The technique of flash photolysis using a dinitrogen laser will be employed to study these intermediates. Another aspect of the research will involve a comprehensive study of the steric and electronic properties of ligands, primarily phosphorus ligands. The approach will involve experimental studies of appropriate series of reactions; compilation of these results and results from a large body of existing literature; and analysis of these data with new statistically valid methods. The end result may be a useful system for effective design of catalysts by using ligands which impart predictable and desirable properties to the catalysts.