Mechanisms of Homogeneous Hydrocarbon Activation and Functionalization by Transition Metal Complexes

在化学部无机、生物无机和有机金属计划的这个项目中，Flood将继续他的研究，即过渡金属络合物如何在均相溶液中形成和断裂C-H、C-C和C-O键。主要的重点将是仔细和基本的机理研究，这应该普遍适用于有机金属化学。这些结果将有助于合理设计碳氢化合物转化为有用化合物的工业催化剂。将继续对过渡金属可溶络合物配位球内碳氢化合物的反应进行综合和机理研究。这项工作将集中在分子间和分子内的C-H活化，金属-碳键中可逆烯烃的插入，以及金属结合的碳和氧中心的α消除和插入。将对金属、氧化态、空间位阻和辅助配体的电子效应、烷基结构、电荷、螯合环大小等因素进行研究。稳定较高氧化态和含氧物种的可能性将通过使用胺连接的有机金属物种而不是更传统的配体来测试。目标体系包括Os、Ir和Pt络合物。在所有情况下，都将通过各种调查对机制进行彻底调查。

In this project in the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division, Flood will continue his studies of how transition metal complexes may form and break C-H, C-C, and C-O bonds in homogeneous solution. The major emphasis will be careful and fundamental mechanistic investigations, which should be generally applicable to organometallic chemistry. These results should be useful in the rational design of industrial catalysts for the transformation of hydrocarbons into useful compounds. Synthetic and mechanistic studies of the reactions of hydrocarbons in the coordination sphere of soluble complexes of transition metals will be pursued. The work will focus on intermolecular and intramolecular C-H activations, reversible alkene insertions into metal-carbon bonds, and alpha-eliminations and insertions at metal-bound carbon and oxygen centers. Metal, oxidation state, steric bulk and electronic effects of ancillary ligands, alkyl group structure, charge, chelate ring size, and other factors will be investigated. The possibility of stabilizing higher oxidation states and oxo-containing species will be tested by use of amine-ligated organometallic species rather than more conventional ligands. Targeted systems include Os, Ir, and Pt complexes. In all cases a thorough investigation of mechanisms will be conducted through a variety of probes.