Alkane Carbonylation and Aldehyde Decarbonylation Catalyzed by Low-Valent Transition Metal Complexes

该项目由无机化学、生物无机化学和有机金属化学计划资助，致力于烷烃羰化催化剂的机理开发和乙醛脱羰反应的反向过程。将研究开发催化体系的几种方法，包括基于新的自由基光化学和热体系、光化学激活的反式羰基氯双(三甲基膦)Rh(I)以及其他热激活的Rh和Ru化合物。本课程将利用实验和理论两种方法进行催化剂设计。在温和的条件下，碳氢化合物的选择性官能化仍然是现代化学最重要但难以实现的目标之一。碳氢化合物选择性和高能效反应的技术影响是巨大的。有机金属化学家最近的发现表明，某些过渡金属络合物在温和的条件下会与碳氢化合物发生反应。该项目将尝试扩展这些早期的研究，以产生催化循环，在催化循环中，金属碳氢化合物与一氧化碳反应生成醛，这些醛可以作为各种其他类型化合物的前体。

This project, funded by the Inorganic, Bioinorganic and Organo- metallic Chemistry Program, deals with the mechanistic based development of catalysts for alkane carbonylation and the reverse process, aldehyde decarbonylation. Several approaches to the development of catalytic systems will be studied including novel radical-based photochemical and thermal systems, photochemically activated trans-carbonylchloro- bis(trimethylphosphine)rhodium(I), and other thermally activated compounds of rhodium and ruthenium. Both experi- mental and theoretical approaches to catalyst design will be utilized. %%% Selective functionalization of hydrocarbons under mild conditions remains as one of the most significant, but elusive, goals of modern chemistry. The technological implications of selective, and energy-efficient reactions of hydrocarbons are enormous. Recent discoveries by organo- metallic chemists have indicated that certain transition metal complexes will react with hydrocarbons under mild conditions. This project will attempt to extend these earlier studies to generate catalytic cycles in which metallated hydrocarbons react with carbon monoxide to produce aldehydes, which can serve as precursors to a wide variety of other types of compounds.