离子型膦配体及其离子型过渡金属配合物的合成和均相催化作用

Synthesis of Ionic Phosphines and Corresponding Ionic Transition Metal Complexes and Their Applications in Homogeneous Catalysis

与传统中性叔膦配体构建的过渡金属配合物相比,由离子型膦配体配位构建的过渡金属配合物具有典型的离子盐组成特点、独特的电子效应和几何构型。该类配合物中,不仅存在金属和配体间的配位作用,还存在正电荷的强吸电子效应和阴阳离子的静电作用,由此可以产生独特的催化性能。近年来,离子型过渡金属配合物的合成及其均相催化应用成为配位化学和均相催化研究中备受关注的领域。离子型过渡金属配合物的离子盐结构,使其在与室温离子液体溶剂结合使用时,离子型离子配体及其配合物能够严格被锁定在离子液体相,具有避免离子型离子配体及其配合物的流失、抑制其失活、并实现循环使用的优点,也成为均相催化固载化的绿色方法之一。本文综述了近十年发展的一类咪唑鎓基与膦配体中的磷原子毗邻的离子型膦配体的合成,及其相应Rh、Pd、Ru、Pt、Au、Ni、Cu等离子型配合物的构建,并介绍了它们在均相催化反应中的应用。

Compared to the traditional neutral phosphine-ligated transition metal complexes（ PTMCs）,the ionic phosphine-ligated ones as the ionic salts are composed with the ion-pairs with unusual electronic effect and varied structural configurations. In these ionic PTMCs,not only the coordinating interaction but also the strong electronwithdrawing effect of the positive-charge and the electrostatic interaction between cations and anion are involved which correspond to the unique catalytic performance. In recent decade,the study on the ionic PTMCs has been concerned as a hot topic in coordination chemistry and homogeneous catalysis. In addition,when the ionic PTMCs are used as the catalysts in combination with the room temperature ionic liquids（ RTILs,as the solvents） for catalytic reactions,the advantages such as the available recovery and recyclability of the catalysts,and the avoided catalyst leaching are evidently observed,which endows theses ionic transition metal complexes great potentialapplications in green chemistry. In this review,the syntheses of the ionic phosphines and the corresponding ionic PTMC（ M = Rh,Pd,Ru,Pt,Au,Ni,Cu） and their applications for homogeneous catalysis,which have been developed in the past ten years,are summarized.