Activation and Functionalization of Hydrocarbons by Soluble Transition Metal Complexes

Thomas C. Flood博士，南加州大学化学系，得到化学学部无机、生物无机和有机金属项目的支持，并得到数学和物理科学理事会多学科活动办公室的仪器支持，用于研究可溶过渡金属配合物对碳氢化合物的活化和功能化。研究将集中在烯烃插入和碳氢活化通过金属介导的氧化加成和亲电烷烃复分解。使用铑、铱、钌和锇的三胺连接配合物，将评估金属、氧化态、立体体积、辅助配体的电子效应、烷基结构、电荷和螯合环大小对这些反应的影响。胺结扎将被用于制备高氧化态和含氧物质，这些物质将显示出增强的功能化碳氢化合物的能力。在所有情况下，都将分析反应机理。碳氢化合物的化学转化是我们利用能源和物质自然资源的基础，而能源和自然资源又是我们经济的一个组成部分，是我们生活水平的一个重要来源。碳氢化合物的许多转化是通过它们与金属和金属化合物的相互作用进行的。化学的一个基本原理是，对反应机制的更好理解将导致改进将原材料转化为材料的方法，从而改善我们的生活。尽可能广泛地表达，所提出的研究的目的是加强和扩展我们对金属配合物如何用于操纵碳氢化合物结构的理解，这最终将导致能源资源的可用性提高。

Dr. Thomas C. Flood, Department of Chemistry, University of Southern California, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division with a contribution for instrumentation from the Office of Multidisciplinary Activities of the Mathematical and Physical Sciences Directorate for the study of the activation and functionalization of hydrocarbons by soluble transition metal complexes. Investigations will focus on alkene insertion and carbon-hydrogen activation through metal mediated oxidative addition and electrophilic alkane metathesis. Using triamine-ligated complexes of rhodium, iridium, ruthenium, and osmium, the influence of metal, oxidations state, steric bulk, electronic effects of the ancillary ligands, alkyl group structure, charge, and chelate ring size on these reactions will be assessed. Amine ligation will be exploited to prepare high oxidation state and oxo species that will display an enhanced ability to functionalize hydrocarbons. In all cases reaction mechanisms will be analyzed. Chemical transformations of hydrocarbons are the basis for much of our utilization of energy and material natural resources, which are in turn an integral part of our economy and an important source of our standard of living. Many transformations of hydrocarbons are carried out through their interactions with metals and metal compounds. It is a basic tenant of chemistry that a better understanding of mechanisms of reactions will lead to improved methods for converting raw materials into materials to improve our lives. Expressed as broadly as possible, it is the purpose of the proposed research to enhance and extend our understanding of how metal complexes can be used to manipulate the structures of hydrocarbons, which should ultimately lead to enhanced availability of energy resources.