Sotorrios Lia, Miloserdov Fedor M, Pécharman Anne-Frédérique, Lowe John P, Macgregor Stuart A, Mahon Mary F, Whittlesey Michael K
Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK.
Department of Chemistry, University of Bath, Bath, BA2 3QD, UK.
Angew Chem Int Ed Engl. 2022 May 2;61(19):e202117495. doi: 10.1002/anie.202117495. Epub 2022 Mar 14.
The syntheses, reactivity and electronic structure analyses of [Ru(PPh ) (ZnMe) H ], 1 a, and [Ru(PPh ) (ZnPh) H ], 2 b, are reported. 1 a exhibits an 8-coordinate Ru centre with axial phosphines and a symmetrical (2 : 2) arrangement of ZnMe ligands in the equatorial plane. The ZnMe ligands in 1 a undergo facile, sequential exchange with ZnPh to give 2 b, which shows a 3 : 1 arrangement of ZnPh ligands. Both 1 a and 2 b exist in equilibrium with their respective 3 : 1 and 2 : 2 isomers. Mechanisms for ZnMe/ZnPh exchange and isomerisation are proposed using DFT calculations. The relationships of these {Ru(ZnR) H } species to isoelectronic Group 8 transition metal polyhydrides and related Schlenk equilibria in the Negishi reaction are discussed.
报道了[Ru(PPh ) (ZnMe) H ]（1 a）和[Ru(PPh ) (ZnPh) H ]（2 b）的合成、反应活性及电子结构分析。1 a呈现出一个具有轴向膦配体的8配位Ru中心，且在赤道平面上ZnMe配体呈对称的（2 : 2）排列。1 a中的ZnMe配体可与ZnPh轻松地依次发生交换，生成2 b，其显示出ZnPh配体的3 : 1排列。1 a和2 b均与其各自的3 : 1和2 : 2异构体处于平衡状态。利用密度泛函理论计算提出了ZnMe/ZnPh交换和异构化的机理。讨论了这些{Ru(ZnR) H }物种与等电子的第8族过渡金属多氢化物以及根岸反应中相关的施伦克平衡之间的关系。
