廉价金属均相催化新策略：氧化还原活性配体催化剂反应机理的理论研究

Building an environment-friendly and efficient homogeneous catalytic system has always been the goal pursued by chemists. Redox active ligands utilize their special metal ligand cooperation process to link the characteristics of base metal centers with the process of homogeneous catalysis, which can achieve the win-win situation both in the catalytic activity and cost. It has important scientific significance and broad application prospect. However, due to the restriction of experimental research methods, there are many problems and deficiencies in mechanistic research at present, hindering further understanding of such catalysts. This project will use quantum chemistry and computational chemistry to study the different functionalities of redox ligands as the entry point. Combining the characteristics of cheap metals, a complete reaction mechanism framework will be established from the microscopic level. Important influencing factors will be summarized, and the special phenomena observed will be explained. This project is expected to provide theoretical guidance for the design of new types of highly efficient and inexpensive homogeneous catalytic systems.

构建低成本且环境友好的高效均相催化体系一直是化学科研工作者所追求的目标。氧化还原活性配体利用其特殊的金属配体协同反应机制，将廉价金属中心自身特性和均相催化反应过程有效的衔接起来，从而实现经济成本和催化活性的双赢，因此具有重要的科学意义和广阔的应用前景。然而受到目前实验研究手段的制约，在机理研究层面存在着诸如机理框架不完善，影响因素复杂等问题，阻碍着人们对此类催化体系的进一步认识。本项目将利用量子化学和计算化学手段，以氧化还原活性配体的不同功能性为研究切入点，从微观层面建立完善的反应机理框架，归纳重要的影响因素，对活性中间体复杂的电子结构进行阐明，解释实验中所观测的特殊现象，从而为设计新型的高效廉价均相催化体系提供理论指导。

本项目以氧化还原活性配体催化剂为研究对象，对其内在催化机制和影响因素进行了系统研究，并在理论层面对催化剂进行了理性设计，取得了一系列原创性的成果并拓展了其它研究方向。通过理论计算系统研究了一系列氧化还原活性配体催化的反应路径，构建了基本的机理类型框架，针对金属中心和功能性配体两个方面，从微观层面系统归纳了氧化还原活性配体催化体系的影响因素，阐明了金属中心电子结构以及氧化态对催化剂驱动力的影响，提出了功能配体效应和旁观配体效应等新观点，在理论层面设计的催化剂在其他课题组的后续研究中得到了验证和支持。这些研究成果有望为设计新型高效廉价的均相催化剂提供理论指导。本项目圆满的完成了项目成果指标的要求，资助研究成果在Organic Letters, Journal of Catalysis, Catalysis Science & Technology, Molecular Catalysis, Inorganica Chimica Acta等国际著名学术期刊上发表标注的SCI 论文共7篇，会议论文4篇；参加国内学术会议并做墙报展示4人次；培养研究生6人。