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

该项目由无机、生物无机和有机金属化学项目资助，研究基于机理的烷烃羰基化催化剂和反过程乙醛脱羰基化催化剂。将研究几种发展催化系统的方法，包括新的基于自由基的光化学和热系统，光化学活化的反式羰基氯-双（三甲基膦）铑(I)，以及其他热活化的铑和钌化合物。催化剂的设计将采用实验和理论两种方法。碳氢化合物在温和条件下的选择性功能化仍然是现代化学最重要但又难以实现的目标之一。碳氢化合物的选择性和高能效反应的技术含义是巨大的。有机金属化学家最近的发现表明，某些过渡金属配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，其中金属化碳氢化合物与一氧化碳反应产生醛，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.