Organometallic Reactions Relevant to Hydrocarbon Functionalization

该奖项在无机，生物无机和有机金属化学项目中支持华盛顿大学的Karen Goldberg教授对基本有机金属反应的详细机理理解，这些反应在碳氢化合物到功能化有机物的选择性催化转化中有潜在的应用。通过对选定的模型反应的研究，这些反应步骤的关键变量将被确定。有关特定配位环境、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。建议研究Pt(II)/Pd（II）配合物活化C-H键、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）配合物的反应活性、Pt（II）上的烯烃插入和-氢化物消除反应。所有这些都具有很高的内在价值，在发展基础知识和建立追求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。开发将碳氢化合物直接转化为更通用的化学品的有效方法，并在这种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，带来成本更低的原料和氧化剂、更低的能源消耗、更低的资本成本、更少的反应步骤和产品分离，以及更少的体积和更少的有毒废物生产。此外，有关利用金属选择性激活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提供新的选择，用于生产特殊化学品和复杂的药物和有机材料的分子合成。在这个项目中，研究生、博士后助理和本科生将学习有机金属反应，并在先进的实验室技术和许多分析和光谱方法的使用方面变得高度熟练。

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.