Energetics and Mechanisms of Organometallic Reactions Relevant to the Functionalization of Alkanes

该奖项在无机，生物无机和有机化学 该计划为能量学研究提供持续的支持， 与功能化相关的有机金属反应机理 凯伦·I博士的研究戈德堡，化学系，大学 在华盛顿。 该项目涉及Pt（II）/Pt（IV）对的研究 作为D8正方形平面和D 6八面体化合物的一般模型， 以及该偶对对烷烃的催化潜力 功能化 氧化还原的机理和动力学研究 在Pt（II）上加成C-H和C-C键并还原消除C-X （X =杂原子、H或C）键将从Pt（IV）进行。 还将进行机制研究，以确定理想的 促进Pt（II）氧化所需的配体/金属环境 通过水或醇与烷基反应以形成Pt（IV）烷基氢氧化物或烷氧化物 和氢气。 Pt（IV）醇盐的反应性也将被探讨 作为高价后过渡金属醇盐的代表。 的 将检查Pt（IV）上的开放配位位点的反应性。 等 一个位点是还原消除反应所必需的， 用于功能化。 可能的协调和插入 小的有机分子和C-H激活的开放网站将是 探讨了 该项目将提供有关激活的基本信息， 烷烃的功能化，并提供可能的新的过渡金属 这一重要反应的催化剂。 烷烃代表了相当大的 我们的天然气和石油资源。的潜力 这些用于大规模化学合成的巨大储量， 受限于烷烃C-H和C-C键的非常不反应的性质。 过渡金属已被证明能够活化C-H 链烷烃中的键和均相过渡金属催化被视为 一种有前途的解决方案，将烷烃选择性转化为更多的 可用的有机产品，如甲烷转化为甲醇。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry program provides continued support for studies on the energetics and mechanisms of organometallic reactions relevant to the functionalization of alkanes by Dr. Karen I. Goldberg, Department of Chemistry, University of Washington. This project involves studies on the Pt(II)/Pt(IV) couple as a general model for d8 square planar and d6 octahedral compounds as well as for the catalytic potential of this couple for alkane functionalization. Mechanistic and kinetic investigations of oxidative addition of C-H and C-C bonds to Pt(II) and reductive elimination of C-X (X = heteroatom, H, or C) bonds from Pt(IV) will be carried out. Mechanistic studies will also be performed to determine the ideal ligand/metal environment required to promote the oxidation of Pt(II) alkyls by water or alcohols to form Pt(IV) alkyl hydroxides or alkoxides and hydrogen. The reactivity of Pt(IV) alkoxides will also be explored as representative of high valent late transition metal alkoxides. The reactivity of an open coordination site on Pt(IV) will be examined. Such a site is necessary for reductive elimination reactions and may also be useful for functionalization. Possible coordination and insertion of small organic molecules and C-H activation by the open site will be explored. This project will give fundamental information on the activation and functionalization of alkanes and provide possible new transition metal catalysts for this important reaction. Alkanes represent a considerable portion of our natural gas and petroleum resources. The potential of these enormous reserves for use in large scale chemical syntheses is limited by the very unreactive nature of the alkane C-H and C-C bonds. Transition metals have been shown to be capable of activating the C-H bonds in alkanes and homogeneous transition metal catalysis is viewed as a promising solution to the conversion of alkanes selectivity into more usable organic products, such as the conversion of methane into methanol.