异双核过渡金属配合物的合成及催化相关反应性的研究

本项目拟通过过渡金属促进的含N-大位阻取代基或多齿配体亚胺的炔基金属关环制备基于双配位卡宾稳定的异双核金属配合物做为研究异双金属催化的模型配合物。考察其中异双金属间的相互作用情况，并测试这些金属配合物的反应活性。重点研究异双核金属中双金属协同效应对反应活性的影响，特别是对转金属过程的影响。测试的反应包括：1）被还原试剂还原成低价双核金属及其氧化加成反应；2）转金属/氧化反应；3）卤代芳烃的氧化加成及含不饱和键的亲核试剂的环化；4）含不饱和键的烯烃的环化；5）小分子活化。对这些异双核金属配合物的结构解析以及对它们反应活性的研究，可以丰富金属有机化学中的卡宾金属化学及对双金属协同效应的认识，可以帮助我们更好地理解相关反应催化机理，有利于发展基于异双核金属催化的新反应。

This project is aimed at synthesizing ditopic heterobinuclear NHC complexes by transition metal-promoted cyclization of metal acetylides containing imine groups with either sterically demanding N-subsituent or multidentate donor group. These heterobinuclear NHC complexes will be used as model complexes for investigating the mechanism of such heterobinuclear metal catalysis. We’ll investigate the interaction effect between two metals, and test their activities. Our study focus on cooperative behavior between two metals on different reactivities, especially on transmetalation process. The model reactions we’ll test include: 1) the reduction of heterobinuclear complexes and the oxidative addition of the resulting low valent complexes; 2) transmetalation/ oxidative addition; 3) oxidative addition of aryl halides and cyclizaton of unsaturated compounds with a nucleophile; 4) cyclization of enyenes; 5) activation of small molecules. Combination of analyses on the structures of these heterobinuclear complexes with the investigation of their reactivities could enrich not only the carbene chemistry but also the insight on the cooperative behavior between metals. It would help us better understand the mechanism of the related catalytic reactions, and will do benefit to develop the new reactions based on heterobinuclear catalysts.