Kinetics and Mechanisms of Organometallic Reactions

在这项研究中，无机，生物无机和 有机化学程序，西奥多L。布朗的 伊利诺伊大学厄巴纳-香槟分校将进行调查 有机金属反应的动力学和机理。的 重点将主要放在过渡金属羰基络合物上， 特别是反应中间体的性质 在有机金属反应过程中形成。这些研究 对有机体的基本理解很重要 金属化学和涉及有机的催化过程， 金属化合物 要研究的一类反应中间体是金属 羰基，具有奇数个电子 （通常是十七或十九）在金属价轨道。一 第二类中间体通过失去配体而形成， 通常是一氧化碳，与金属结合。技术 使用二氮激光器的闪光光解将被用来 研究这些中间体。研究的另一个方面将 涉及空间和电子的综合研究 配体，主要是磷配体的性质。的 方法将涉及适当的实验研究 一系列反应;这些结果和结果的汇编 从大量的现有文献;和分析这些 新的统计有效的方法。最终结果可能 是一个有用的系统，通过使用有效的催化剂设计 这些配体赋予可预测的和期望的性质， 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.