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

这个无机、生物无机和有机金属化学奖项为华盛顿大学化学系Karen I. Goldberg博士对与烷烃功能化相关的有机金属反应的能量学和机制的研究提供了持续的支持。该项目涉及Pt(II)/Pt（IV）偶对作为d8方平面和d6八面体化合物的一般模型，以及该偶对烷烃功能化的催化潜力的研究。将进行C-H和C-C键在Pt（II）上的氧化加成以及C-X （X =杂原子，H或C）键在Pt（IV）上的还原消除的机理和动力学研究。还将进行机理研究，以确定促进Pt（II）烷基被水或醇氧化形成Pt（IV）烷基氢氧化物或烷氧化物和氢所需的理想配体/金属环境。Pt（IV）醇氧化物作为高价晚期过渡金属醇氧化物的代表，其反应性也将进行探讨。将考察Pt（IV）上一个开放配位位点的反应性。这种位点对于还原消除反应是必需的，也可能对功能化有用。将探索小有机分子可能的配位和插入以及开放位点的碳氢活化。该项目将为烷烃的活化和功能化提供基础信息，并为这一重要反应提供可能的新的过渡金属催化剂。烷烃在我们的天然气和石油资源中占相当大的一部分。这些巨大的储量用于大规模化学合成的潜力受到烷烃碳氢键和碳碳键非常不活跃的性质的限制。过渡金属已被证明能够激活烷烃中的C-H键，均相过渡金属催化被视为将烷烃选择性转化为更有用的有机产物的有希望的解决方案，例如将甲烷转化为甲醇。

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.