Organometallic Chemistry of Carbon Dioxide

该奖项来自无机、生物无机和有机金属化学项目，将支持有机金属化学一般领域的研究，特别强调有机金属化合物促进二氧化碳的反应。人们对这类反应的实际兴趣源于二氧化碳在未来很有可能被用作化学合成的碳源。例如，在与氢的反应中，由太阳能分解水产生。该项目的长期目标是对二氧化碳插入M-H、M-C和M-O键所产生的碳-氢、碳-碳和碳-氧键形成过程有一个清晰的机制观点。反应性研究表明，阴离子八面体金属衍生物与中性方形平面金属配合物的碳氢键和碳碳键形成反应具有相似的反应特征。研究进一步表明，从研究发生在单个金属中心的这些不同过程中获得的知识可转移到可能发生两种反应类型的金属中心。从过渡金属-二氧化碳化学中获得的见解将用于探索二氧化碳作为有机化学品合成原料的潜在用途。要探索的具体领域包括金属甲酸酯和碳酸酯的脱羧机制，低价金属的烷基、芳基和硅基氧化物化学，与碳氢化合物活化和功能化有关的研究，以及涉及二氧化碳的催化过程。

This award from the Inorganic, Bioinorganic and Organometallic Chemistry Program will support research in the general area of organometallic chemistry, with particular emphasis on reactions of carbon dioxide promoted by organometallic compounds. The practical interest in such reactions derives from the strong possibility that carbon dioxide will be used as a source of carbon for chemical synthesis in the future, in for example reactions with hydrogen derived from the decomposition of water by solar energy. The long-term goal of the project is a clear mechanistic view of carbon-hydrogen, carbon-carbon and carbon-oxygen bond forming processes resulting from the insertion of carbon dioxide into M-H, M-C and M-O bonds. Reactivity studies have revealed a similarity in reaction characteristics for carbon-hydrogen and carbon-carbon bond forming reactions involving anionic octahedral metal derivatives and neutral square-planar metal complexes. It has further been shown that knowledge gained from investigating these different processes occurring on individual metal centers is transferable to metal centers where both reaction types are possible. The insight gained from transition metal-carbon dioxide chemistry will be used in exploring potential uses of carbon dioxide as a feedstock for the synthesis of organic chemicals. Specific areas to be explored include decarboxylation mechanisms of metallo-formates and -carbonates, alkyl-, aryl- and silyl-oxide chemistry of low-valent metals, studies related to C-H activation and functionalization, and catalytic processes involving carbon dioxide.