N-杂卡宾金属配合物MOFs的制备及非均相催化CO2转化研究

Our subject aims to develop novel heterogeneous chiral and achiral catalysts to solve the problem of high-valued and efficient conversion of CO2, especially the asymmetric catalysis of CO2, based on the idea of "green chemistry" and sustainable development. A series of new chiral and achiral N-heterocyclic carbene metal complex ligands containing multicarboxyl are synthesized. New organic/inorganic hybrid chiral/achiral metal-organic frameworks supermolecular crystal materials, which have specific network topology structures, are synthesized by hydrothermal or solvothermal method starting from N-heterocyclic carbene metal complex ligands and metal salts. Then using this materials as molecular reactor, making use of specific micropore and active sites catalyze a series of reactions involving CO2 under mild conditions, especially the asymmetric reactions of CO2. We hope to achieve the product in high yield, high ee values. Then we explore the relationship between the material micropore structure and catalytic activity and realize the recycle of catalysts many times. Finally these excellent chiral/ achiral heterogeneous catalysts are obtained, which can lay the foundation for industrialization of CO2. The completion of the subject will provide a new approach and strategy for the preparation and application of heterogeneous chiral/achiral catalytic materials and high-valued and efficient conversion of CO2, in accordance with the idea of "green chemistry", the subject is significant to the theoretical research and practical applications.

本着“绿色化学”和可持续发展的理念，本课题旨在发展新型非均相手性和非手性催化剂，解决CO2的高值、高效转化问题，尤其是CO2的不对称催化问题。首先合成一系列新型手性和非手性多羧基氮杂卡宾金属配合物配体，然后利用该配体与金属盐通过水热或溶剂热合成具有特定网络拓扑结构的新型有机/无机杂化手性和非手性金属有机框架超分子晶体材料，使其作为分子反应器，利用其特殊孔洞结构及催化位点吸附并在温和条件下催化一系列有CO2参与的反应，尤其是不对称反应，期望实现产物高产率、高ee值。探讨材料微观结构与催化活性之间的关系，并实现催化剂的多次循环使用，最终获得性能优良的手性和非手性非均相催化剂，为CO2的工业化应用打下一定的基础。本课题的完成，为非均相催化材料的制备及CO2高值转化提供一种新的方法和策略，符合“绿色化学”发展理念，因此该课题具有重要的理论意义和应用价值。

金属有机框架(MOFs)是金属离子或金属簇与有机配体通过自组装形成的一种结构稳定，具有一定孔洞，结构可调的晶体材料。因其独特的结构特性受到广泛关注。本项目设计合成两个手性金属salen配体Ni(II)-Salen 和Cu(II)-Salen，该配体再分别与硝酸锌溶剂热反应合成MOF 1和MOF 2。MOF 1高效催化环氧化物与CO2的扩环反应生成环状碳酸酯，以及水相中过氧化氢选择性氧化末端烯烃；MOF 2水相中高效催化苄醇的选择性氧化。催化剂可多次循环使用，活性基本不变。本文基于金属Salen配体MOFs材料的制备及催化性能研究，为非均相催化剂的制备及应用提供一种可能。. 此外，发展了一系列新型氮杂卡宾咪唑鎓盐配体，并构建了一系列新型氮杂卡宾铜、银和钯配合物，进一步丰富了过渡金属催化剂种类。以合成的新型氮杂卡宾金属配合物为催化剂成功催化温和条件下Chan-Lam偶联反应、氯代芳烃参与的大位阻Suzuki-Miyaura偶联反应以及一锅法高效合成呋喃和噻吩衍生物，所发展的方法操作简单且绿色高效，更加符合“绿色化学”的理念。. 采用新方法制备Cu/MIL-101非均相催化剂，制备的Cu/MIL-101催化剂具有形貌好，性质稳定，催化活性高的特点。能高效催化三组分反应，以较高产率合成1,2,3-三唑类、1,3-丁二炔类、β-酮膦酸酯类、吲嗪类及丙炔胺类衍生物，该类反应具有操作简单、对环境友好、原子经济性强等特点。.