基于酰胺键构建的钌配合物的合成及其金属-配体协同催化机制研究

Amide bond is an important chemical bond in organic chemistry. Latest developed direct synthesis of amide from alcohol and amine by extrusion of dihydrogen is a green approach to construct amide bond. While, catalysts for the "green approach" are limited. Development of effective catalyst is extremely important for exploration of the atom-economic reaction. Moreover, understanding the reaction mechanism will help to develop high efficient catalyst. In this project, a) a series of tridentate, bidentate ligands with different weak donors based on pyridine skeleton and their corresponding ruthenium complexes will be synthesized; b) the dearomatization-aromatization process and the metal-ligand cooperative catalysis mechanism will be studied by the stoichiometric reaction of ruthenium complex with small molecules such as hydrogen, alcohol and amine; c) the relationship between ligands and catalytic activities also will be investigated by applying the ruthenium complexes in alcohol/amine dehydrogenation. Based on the mechanism study, a class of high effective catalysts for direct amide synthesis from alcohol and amine with liberation of hydrogen is expected to be synthezized. Moreover, application of the catalysts in the synthesis of amides and polyamides is anticipated to be realized.

酰胺键在有机化学中是一种重要的化学键，醇-胺脱氢直接合成酰胺是近期发展起来的绿色酰胺键构建方法。然而，适用于酰胺键绿色构建的催化体系较少。设计和开发高效的催化体系对于发展此类原子经济性反应具有重要意义，对反应机理的理解将有助于设计和开发高效的催化体系。本项目拟：1）基于吡啶骨架设计、合成一序列具有不同弱供电体的三齿配体钌配合物、以及不同结构的两齿配体钌配合物，考察它们的"去芳香化-芳香化"能力；2）通过钌配合物与氢气、醇、胺等小分子的化学计量反应，研究金属-配体协同催化机理；3）通过钌配合物催化的醇（胺）的脱氢反应，探讨配体结构与钌配合物催化活性的关系。从而开发出一类适用于醇-胺脱氢高效合成酰胺的新催化剂体系，并成功地将其应用于酰胺、聚酰胺的合成。

酰胺键在有机化学中是一种重要的化学键，醇-胺脱氢直接合成酰胺是近期发展起来的绿色酰胺键构建方法。然而，适用于酰胺键绿色构建的催化体系较少。具有金属配体协同催化能力的钌基配合物是一类潜在的催化醇-胺脱氢构建酰胺键的催化剂。本项目合成了一系列含氮侧臂的三齿配体及其金属钌配合物，并对这些配合物进行了完整的结构表征；探讨了该类配合物的芳香化-去芳香化能力以及其对醇的脱氢能力；结合膜反应器实现了低沸点醇和胺的直接脱氢偶联构建酰胺键；通过DFT计算研究了该类配合物的金属-配体协同催化过程。该项目的完成进一步充实了具有金属-配体协同催化能力的催化剂体系，也为低沸点醇-胺脱氢偶联构建酰胺键提供了一种有效的方法。