钌-膦-二胺配合物的电子效应对选择氢化C=C和C=O键的影响

本文合成了一系列新的钌-膦-二胺配合物，并通过核磁和元素分析表征确定了配合物的组分和结构。文中进一步考察了这些配合物用于苄叉丙酮以及苯乙酮和苯乙烯组成的混合物的选择催化加氢，发现随着膦和二胺配体中配位原子碱性的增强，羰基加氢的活性和选择性大幅提高；反之，配位原子碱性减弱不仅降低反应活性，羰基加氢的选择性也大幅降低。基于这些配合物的电子效应对催化氢化性质的影响，我们提出了在钌-膦-二胺体系中的氢活化机理。

Effect of Electronic Factor in Ru‐phosphine‐diamine Complexes on Selective Hydrogenation of CC and CO Bonds

A series of ruthenium complexes bearing different phosphines and diamines were synthesized and their components and structures were characterized by NMR spectra and elemental analyses. The catalytic properties of these complexes for the hydrogenation of benzylideneacetone and the mixture of acetophenone and styrene were investigated. The results showed that the basicity increase of phosphine or diamine dramatically facilitates the hydrogenation activity and selectivity to CO double bond. On the contrary, the basicity decrease of phosphine or diamine not only slows down the catalytic activity, but also significantly suppresses the hydrogenation selectivity to CO double bond. Based on the effect of electron factors of these complexes on the hydrogenation activity and selectivity of benzylideneacetone and the mixture of styrene and acetophenone, the activation mechanism of dihydrogen in ruthenium‐phosphine‐diamine system was proposed.