Selective Preparation of a Heteroleptic Cyclometallated Ruthenium Complex Capable of Undergoing Photosubstitution of a Bidentate Ligand
作者:Jordi-Amat Cuello-Garibo、Catriona C. James、Maxime A. Siegler、Samantha L. Hopkins、Sylvestre Bonnet
DOI:10.1002/chem.201803720
日期:2019.1.24
Cyclometallated ruthenium complexes typically exhibit red‐shifted absorption bands and lower photolability compared to their polypyridyl analogues. They also have lower symmetry, which sometimes makes their synthesis challenging. In this work, the coordination of four N,S bidentate ligands, 3‐(methylthio)propylamine (mtpa), 2‐(methylthio)ethylamine (mtea), 2‐(methylthio)ethyl‐2‐pyridine (mtep), and
与它们的聚吡啶基类似物相比,环金属化钌配合物通常表现出红移的吸收带,并且具有较低的光化性。它们还具有较低的对称性,这有时使其合成具有挑战性。在这项工作中,四个N,S二齿配体,3-(甲硫基)丙胺(mtpa),2-(甲硫基)乙胺(mtea),2-(甲硫基)乙基-2-吡啶(mtep)和2的配位-研究了(甲基硫基)甲基吡啶(mtmp)对环金属化前体[Ru(bpy)(phpy)(CH 3 CN)2 ] +(bpy = 2,2'-联吡啶,Hphpy = 2-苯基吡啶)的存在相应的杂配物[Ru(bpy)(phpy)(N,S)] PF 6([ 2 ] PF 6 – [ 5 ] PF分别为6)。合成的立体选择性很大程度上取决于由Ru配位的N,S配体形成的环的大小,其中[ 2 ] PF 6和[ 4 ] PF 6是立体选择性形成的,但是[ 3 ] PF 6和[ 5 ]以不可分离的异构体的混合物形式获得PF 6。通过结合DFT,2D