Oxo-Organometallic Chemistry

这个项目属于无机、生物无机和有机金属化学专业，属于有机金属化学领域，主要研究过渡金属氧配合物是如何形成以及它们是如何反应的。金属氧化物和含氧化合物被广泛用作有机化合物选择性转化的催化剂和试剂，但对大多数这些重要过程的机制知之甚少。该项目的一个主要重点是醇盐和氧烷基配合物的相互转化。为了了解动力学屏障的大小和起源，并确定氢化物、烷基、苯基、烯丙基和其他基团的迁移倾向，这种1,2-迁移将在许多系统中进行探索。在第二个子项目中，氧原子转移的研究将广泛探讨金属-氧多键的稳定性和反应性。氧原子转移反应将用于解决多重键强度如何随金属的性质、氧化态和辅助配体而变化。这种对氧原子转移的热力学理解将与机械研究相结合，重点是理解原子转移的（通常是相当大的）动力学障碍。还将探讨二氧及其相关分子如何形成氧配合物，特别强调四电子氧化加成反应的可能性。

This project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is in the area of organometallic chemistry and is concerned with how transition metal oxo complexes are formed and how they react. Metal oxides and oxo compounds are widely used as catalysts and as reagents for selective transformations of organic compounds, but little is known about the mechanisms of most of these important processes. A major focus of the project is the interconversion of alkoxide and oxo-alkyl complexes. This 1,2-migration will be explored in a number of systems in order to understand the magnitude and origin of the kinetic barriers and to determine the migratory aptitudes of hydride, alkyl, phenyl, allyl and other groups. In a second subproject studies of oxygen atom transfer will probe the wide range of stability and reactivity of metal-oxygen multiple bonds. Oxygen atom transfer reactions will be used to address how multiple bond strengths vary with the nature of the metal, its oxidation state, and the ancillary ligands. This thermodynamic understanding of oxygen atom transfer will be coupled with mechanistic studies, with an emphasis on understanding the (often sizeable) kinetic barriers to atom transfer. Also to be explored is how oxo complexes are formed from dioxygen and related molecules, with special emphasis on the possibility of four-electron oxidative addition reactions.