Organometallic Reactions Relevant to Hydrocarbon Functionalization

无机，生物无机和有机化学计划的这一奖项支持华盛顿大学的Karen Goldberg教授对基本有机金属反应进行详细的机械理解，这些反应在碳氢化合物到官能化有机物的选择性催化转化中具有潜在的应用。通过对选定的模型反应的研究，将确定这些反应步骤的关键变量。有关特定的配位环境，金属和辅助配体的选择，基板的要求和反应条件，有利于特定的反应步骤的信息将划定。建议研究Pt（II）/Pd（II）配合物的C-H键活化、Pt（IV）配合物的还原消除、Pt和Pd烷基与分子氧的反应、五配位Pt（IV）配合物的反应性、Pt（II）上的烯烃插入和氢化物消除反应，在发展基础知识和建立追求有效有机金属的合理发展所需的基础方面都具有很高的内在价值。具有挑战性的有机转化催化剂。开发用于将烃直接转化为更通用的化学品的有效方法以及在这种方法中利用氧作为氧化剂可以从根本上改变化学工业中的实践，其益处是原料和氧化剂成本更低、能耗更低、资本成本更低且反应步骤和产物分离更少、以及产生的废物体积更小且毒性更小。此外，所获得的关于使用金属来选择性活化C-H键并将其转化为新的C-C和C-X键以及使用分子氧作为氧化剂的知识可以为有机化学家提供用于生产特种化学品以及药物和有机材料的复杂分子合成的新选择。在从事这个项目的同时，研究生，博士后和本科生将学习有机金属反应，并在先进的实验室技术和使用众多的分析和光谱方法方面具有很高的技能。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports Professor Karen Goldberg at the University of Washington to develop a detailed mechanistic understanding of fundamental organometallic reactions that have potential application in the selective catalytic transformations of hydrocarbons to functionalized organics. Through investigations of selected model reactions, the critical variables for these reactions steps will be identified. Information concerning specific coordination environments, metal and ancillary ligand options, substrate requirements and reaction conditions that favor particular reaction steps will be delineated. Proposed investigations of C-H bond activation by Pt(II)/Pd(II) complexes, of reductive elimination from Pt(IV) complexes, of reactions of Pt and Pd alkyls with molecular oxygen, of the reactivity of five-coordinate Pt(IV) complexes, of olefin insertion and -hydride elimination reactions at Pt(II), all have high intrinsic value in developing fundamental knowledge and establishing the foundations needed to pursue the rational development of effective organometallic catalysts for challenging organic transformations. The development of effective methodologies for the direct conversion of hydrocarbons to more versatile chemicals and the utilization of oxygen as an oxidant in such processes could fundamentally change practices in the chemical industry with the benefits of lower cost feedstocks and oxidant, lower energy consumption, lower capital costs with fewer reaction steps and product separations, and lower volume and less toxic waste production. In addition, the knowledge gained concerning the use of metals for the selective activation and conversion of C-H bonds into new C-C and C-X bonds and the use of molecular oxygen as an oxidant may provide organic chemists with novel options for application in the production of specialty chemicals and complex molecular syntheses of pharmaceuticals and organic materials. While working on this project, graduate students, postdoctoral associates and undergraduate students will study organometallic reactions and become highly skilled in advanced laboratory techniques and in the use of numerous analytical and spectroscopic methods.