廉价过渡金属催化一氧化碳环加成反应的理论和实验研究

Cycloaddition reaction of CO is one of the most important reactions in organic reactions. The widely applied catalysts for cycloaddition reaction of CO are complexes of noble metals such as Rh,Ru,Pd. In this project, the theoretical and experimental studies of cycloaddition reaction of CO catalyzed by cheap transition metal complexes will be carried out. We will design several types of metal complexes based on cheap transition metals, including Cu, Co, Ni, Fe, as the substitutes of noble metal catalysts, and use theoretical and experimental methods to study their structure and stability, and their catalytic activity, selectivity and reaction mechanism for several typical cycloaddition reactions of CO. Subsequently, we will improve the structures of transition metal complexes according to experimental results and the comparison of the obtained results with the corresponding data for noble metal catalysts. These researches will provide the theoretical basis for the design of new catalysts for cycloaddition reaction of CO.

一氧化碳环加成反应是一类非常重要的有机化学反应。目前普遍采用的催化剂主要为铑、钌、钯等贵金属配合物催化剂。本项目将对廉价过渡金属配合物催化的一氧化碳环加成反应进行理论和实验研究。通过设计几种不同类型的廉价过渡金属，如铜、钴、镍、铁等配合物催化剂作为贵金属配合物催化剂的替代物。采用理论计算化学方法结合实验验证研究它们与贵金属配合物催化剂结构的异同点，考查这些过渡金属配合物催化几种典型的一氧化碳环加成反应的反应机理、反应活性和选择性等，并根据实验结果不断优化这些廉价过渡金属配合物催化剂的结构，得到催化剂结构、稳定性与活性之间的构效关系规律,本项目的实施有望为设计高效的一氧化碳环加成反应催化剂提供理论依据和实验验证。

设计合成了多种铜、钴、镍、铁、金、铂等过渡金属配合物催化剂，采用理论计算化学方法结合实验验证研究它们的结构特征，考查这些过渡金属配合物催化几种典型的化学反应，包括一氧化碳环加成反应、幻化反应、醛的硅氢化反应、C-H键活化反应，的反应机理、反应活性和选择性等，并根据实验结果不断优化这些过渡金属配合物催化剂的结构，得到催化剂结构、稳定性与活性之间的构效关系规律,为设计高效的一氧化碳环加成反应等重要有机化学反应的催化剂提供了理论依据和实验验证。研究成果在SCI期刊上发表论文26篇，培养研究生8人。

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