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

该奖项在无机化学、生物无机化学和金属有机化学项目中继续支持华盛顿大学化学系Karen I.Goldberg博士对与烷烃官能化相关的有机金属反应的能量学和机理的研究。本项目涉及作为d8正方形平面化合物和d6八面体化合物的通用模型的铂(II)/铂(IV)对以及该对对烷烃官能化的催化潜力的研究。将对C-H和C-C键在铂(II)上的氧化加成和C-X(X=杂原子、H或C)键的还原消除进行机理和动力学研究。还将进行机理研究，以确定促进铂(II)烷基被水或醇氧化形成铂(IV)烷基氢氧化物或醇氧化物和氢所需的理想配体/金属环境。以铂(IV)醇盐为代表的高价后过渡金属醇盐的反应性也将被探讨。将考察铂(IV)上开放配位中心的反应性。这样的位置是还原消除反应所必需的，也可能对官能化有用。可能的配位和插入的小有机分子和C-H活化的开放位置将被探索。该项目将为烷烃的活化和官能化提供基础信息，并为这一重要反应提供可能的新型过渡金属催化剂。烷烃占我国天然气和石油资源的相当大一部分。这些巨大的储量用于大规模化学合成的潜力受到烷烃C-H和C-C键非常不反应的性质的限制。过渡金属能够激活烷烃中的C-H键，均相过渡金属催化被认为是一种很有前途的解决方案，可以将烷烃的选择性转化为更有用的有机产品，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.