Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.
J Phys Chem A. 2012 Apr 26;116(16):4029-34. doi: 10.1021/jp211627v. Epub 2012 Apr 12.
A homocoupling reaction mechanism of bromobenzene mediated by the [Ni(cod)(bpy)] (cod = 1,5-cyclooctadiene; bpy = 2,2'-bipyridine) complex was investigated by means of in situ time-resolved X-ray absorption fine structure (XAFS) and factor analysis. A dimer intermediate Ni(bpy)(Ph)Br proposed in the previous studies by other groups is too dilute to observe with the XAFS technique; however, the structures and concentrations on the time course of a reactant [Ni(cod)(bpy)], an intermediate [Ni(bpy)(Ph)Br(dmf)(2)], and a byproduct [Ni(bpy)Br(2)(dmf)] during reaction are revealed by this combination.
通过原位时间分辨 X 射线吸收精细结构（XAFS）和因子分析研究了[Ni(cod)(bpy)]（cod=1,5-环辛二烯；bpy=2,2'-联吡啶）配合物介导的溴苯的偶联反应机理。先前其他研究小组提出的二聚体中间体Ni(bpy)(Ph)Br太稀，无法用 XAFS 技术观察；然而，通过这种组合，可以揭示反应过程中反应物[Ni(cod)(bpy)]、中间体[Ni(bpy)(Ph)Br(dmf)(2)]和副产物[Ni(bpy)Br(2)(dmf)]的结构和浓度随时间的变化。
