Mechanisms of Homogeneous Hydrocarbon Activation and Functionalization by Transition Metal Complexes

过渡金属配合物均相烃活化和功能化机制

• 批准号: 9014531
• 负责人: Thomas Flood
• 金额: $ 27.9万
• 依托单位: University of Southern California
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-12-15 至 1994-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9014531&HistoricalAwards=false
• 关键词: Mechanisms; Homogeneous; Hydrocarbon; Activation; Functionalization

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.

在这个项目中，无机，生物无机， 化学部的有机计划，洪水将 继续研究过渡金属络合物如何形成 并在均相溶液中破坏C-H、C-C和C-O键。 的 重点将是仔细和基本的机械 一般适用于 有机金属化学这些结果应该是有用的， 工业催化剂的合理设计 转化为有用的化合物。 反应的合成和机理研究 可溶性络合物的配位层中的烃 过渡金属将继续使用。 工作重点将放在 分子间和分子内C-H活化，可逆 烯烃插入到金属-碳键中，和 α-消除和插入在金属结合的碳和 氧中心 金属，氧化态，空间体积和 辅助配体的电子效应，烷基结构， 电荷、螯合环大小和其他因素将是 研究了 稳定较高氧化的可能性 状态和含氧物种将通过使用 胺连接的有机金属物种，而不是更多 常规配体。 目标系统包括Os、Ir和Pt 配合物 在所有情况下，彻底调查机制 将通过各种探针进行。