氮杂环卡宾-钯绿色、高效配合物的设计、合成及其构效关系研究

项目名称： 氮杂环卡宾-钯绿色、高效配合物的设计、合成及其构效关系研究

项目编号： No.21471115

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 陆建梅

作者单位： 温州大学

项目金额： 90万元

中文摘要： 针对传统胺化反应采用对空气敏感、有毒、价格昂贵的叔膦-钯配合物体系及最近少量报导的氮杂环卡宾-钯配合物催化剂合成步骤复杂或催化效率不高等难点、热点问题，本项目拟设计、合成系列富电子、大位阻氮杂环卡宾配体，筛选含氮辅助配体，依据配位多面体结构及配位取代反应规律，探寻组装稳定、绿色、高效氮杂环卡宾-钯配合物的简便新途径。采用核磁共振、质谱、元素分析及X-ray单晶衍射等方法进行结构表征后，再结合目标配合物在氯苯与苯胺的偶联反应中的催化效率及量化模拟，进行结构与功能的相关性分析，提出与实验结果一致的更合理的催化机理。以上成果不仅优化了高催化活性氮杂环卡宾-钯配合物的合成路线，提高了其催化效率，丰富了其催化作用的理论基础，而且也将为绿色、高效的合成工艺提供稳定的催化剂。

中文关键词： 过渡金属；金属有机化合物；功能配合物；设计合成；构效关系

英文摘要： In view of traditional amination reactions using air-sensitive, toxic and expensive tertiary phosphine-palladium complexes and recently a few reports using N-heterocyclic carbene-palladium complexes possessing the disadvantages of lengthy synthetic routes or lower catalytic efficiency, in this project, we aim to design and synthesis a series of electron-rich and sterically-hindered N-heterocyclic carbene ligands, and screen some N-containing ancillary ligands. In addition, on the basis of the coordination polyhedron structure and the rules of ligand substitution, we will seek a new route for the synthesis of green, stable and highly efficient N-heterocyclic carbene-palladium complexes. After the structure of the N-heterocyclic carbene-palladium complexes were characterized by NMR, mass spectroscopy, elemental analysis and X-ray single crystal diffraction, their catalytic activity will be evaluated in the coupling reaction of chlorobenzene with aniline. Based on these results and combining the analysis on the structure-activity relationship, a more reasonable mechanism will be given. The above results will not only give optimized route for the synthesis of N-heterocyclic carbene-palladium complexes with high catalytic activity and will also enrich the theory of their catalysis. Furthermore, it will aslo give stable catalysts for the green and efficeint synthetic process.

英文关键词： transition metal;organometallic compounds;functional complexes;design and synthesis;structure-activity relationship