Activation and Functionalization of Hydrocarbons by Soluble Transition Metal Complexes

南加州大学化学系Thomas C.Flood博士得到了化学部无机、生物无机和有机金属计划的支持，数学和物理科学局多学科活动办公室为研究可溶过渡金属络合物对碳氢化合物的活化和功能化做出了贡献。研究的重点将集中在通过金属介导的氧化加成和亲电烷烃歧化来插入烯烃和碳氢活化。使用三胺连接的Rh、Ir、Ru和Om的配合物，将评估金属、氧化状态、空间体积、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。将利用胺连接来制备高氧化态和氧物种，这些物种将显示出增强的碳氢化合物官能化能力。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大量能源和物质自然资源的基础，而这些资源反过来又是我们经济的组成部分和我们生活水平的重要来源。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。更好地了解反应机理将导致改进将原材料转化为材料的方法，以改善我们的生活，这是化学的一个基本用途。尽可能笼统地说，拟议研究的目的是加强和扩大我们对如何利用金属络合物来操纵碳氢化合物结构的理解，这最终应导致提高能源的可获得性。

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.