氮杂环卡宾配合物“嵌入”型共轭多孔聚合物的可控制备及催化应用

Traditonal supported metal-complex catalyzed reactions have some drawbacks,such as unhomogeneous catalytic site and poor recyclability. On the other hand, conjugated microporous or mesoporous polymer (CMP) has good statility toward acid, base, water and heating, which are key points for a good catalyst, furthermore,N-heterocyclic carbene metal complexes (M-NHC) have been successfully applied in many catalytic reactions. Therefore, we herein propose to start this proposal by designing and synthesizing a range of M-NHC monomer with different functionalities, and then achieve the controllable and efficient preparation of M-NHC@CMP catalytic materials by utilizing the strategies of tripolymerization of monomers and catalytic coupling of the monomer with steric linkers.Subsequently, relationships between the structure of M-NHC@CMP and their catalytic activities as well as the stability of reused catalyst will be deeply studied. After the completion of these investigations, a series of M-NHC@CMP porous catalysts will be succesfully synthesized, and some efficient and recyclable carbonylation reaction systems through catalytic insertion of CO2 or CO onto organic molecule to yield carbonyls will also be developed.Hopefully, all these achievements could possibly provide some scientific foundations and new ideas to solve drawbacks of current supported metal-complex catalysts.

针对目前负载型配合物催化中亟待解决的问题，基于共轭微（介）孔聚合物（CMP）具有良好的稳定性以及氮杂环卡宾配合物（M-NHC）已经在多类催化反应中得到了成功的应用,本项目拟从具有不同官能团（乙炔、氰基、乙酰、溴或碘）、尺寸大小的氮杂环卡宾配合物单体的设计合成出发，运用分子间单体官能团的三聚反应或将单体与刚性的骨架切块催化偶联的自负载策略，实现催化活性位均一"嵌入"型共轭多孔金属有机催化材料（M-NHC@CMP）的可控与高效制备，进而系统研究材料的骨架类型、比表面积、孔结构等结构特点与催化活性以及催化剂循环使用情况间的关系，揭示其构效关系，发展出催化效率高、循环使用稳定性好的新一代多孔催化材料，构建其催化的二氧化碳、一氧化碳插入有机小分子生成相应羰基化合物的高效非均相催化反应新体系，为解决现有负载型配合物催化剂存在的活性位点不均、稳定性差等不足提供新的思路和科学基础。

本课题将均相催化剂中配体对金属中心的电子和空间调控理念与多相催化剂活性位的均匀构建以及多功能催化剂制备有机地结合起来，制备了一系列对酸碱变换、光以及二氧化碳响应的新型智能氮杂卡宾金属小分子配合物催化剂，利用叠氮与炔烃双官能团化的氮杂卡宾配合物分子间自催化“click”偶联合成了一类二十多个链状异金属有序相邻的氮杂卡宾配合物聚合物催化剂，基于碘官能团化的氮杂卡宾与多齿炔烃单体制备了一类氮杂卡宾金属配合物嵌入型的类分子筛多孔聚合物催化剂，同时又制备了多类催化活性位高分散的纳米金属催化材料。这些催化剂在羰基化、加氢以及串联反应合成含羰基化合物、氮杂环化合物、生物基化学品等中表现出了较高的催化活性，该课题的顺利实施为特定C-H、C-C以及C-O键的活化与定向转化、生物基乙酰丙酸与糠醛的转化以及含杂环精细化学品的均多相合成理性设计制备高效、高稳定的催化剂提供了重要借鉴。