Organometallic Reactions Relevant to Hydrocarbon Functionalization

无机化学、生物无机化学和金属有机化学项目的这一奖项支持华盛顿大学的Karen Goldberg教授对基本的有机金属反应进行详细的机理理解，这些反应在碳氢化合物的选择性催化转化为官能化有机物方面具有潜在的应用。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。关于特定配位环境、金属和辅助配体选择、底物要求和有利于特定反应步骤的反应条件的信息将被描述。所提出的关于铂(II)/钯(II)络合物活化C-H键的研究，从铂(IV)络合物的还原消除，铂和钯的烷基与分子氧的反应，五配位的铂(IV)络合物的反应活性，铂(II)上的烯烃插入和氢化物消除反应的研究，都在发展基础知识和建立合理开发有效的有机金属催化剂以挑战有机转化所需的基础方面具有很高的内在价值。开发有效的方法将碳氢化合物直接转化为更多用途的化学品，并在这类过程中利用氧气作为氧化剂，可以从根本上改变化学工业的做法，其好处是原料和氧化剂成本更低、能源消耗更低、反应步骤和产品分离更少、资本成本更低、产量更低和有毒废物更少。此外，利用金属选择性地活化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，可能为有机化学家在特种化学品的生产和药物和有机材料的复杂分子合成中提供新的应用选择。在这个项目的工作中，研究生、博士后助理和本科生将学习有机金属反应，并在高级实验室技术和大量分析和光谱方法的使用方面变得非常熟练。

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.