Fernández-Moyano Sara, Peñas-Defrutos Marconi N, Bartolomé Camino, Espinet Pablo
IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, Valladolid-47071, Spain.
Chem Commun (Camb). 2021 Jan 5;57(1):125-128. doi: 10.1039/d0cc06450e.
Aryl rearrangements triggered by Cl- extraction from trans-[AuIII(Rf)2Cl2]- (Rf = C6F3Cl2-3,5), led quickly to a mixture of [Au(Rf)3(solv)], cis-[Au(Rf)2Cl(solv)] and [Au(Rf)Cl2(solv)] (solv = OEt2, OH2). 19F NMR and X-ray diffraction studies led us to identify the species present in solution and the role of the solvent in their formation, while DFT calculations confirm the thermodynamic basis of their evolution. Very different Rf-Rf coupling rates are found from (μ-Cl)2[cis-Au(Rf)2]2 or cis-[Au(Rf)2ClL] species (L = OEt2, NCMe, Cl-) depending on the coordination strength of the ligand or solvent in the fourth position.
从反式 - [AuIII(Rf)2Cl2]-（Rf = C6F3Cl2 - 3,5）中提取Cl-引发的芳基重排反应迅速生成了[Au(Rf)3(solv)]、顺式 - [Au(Rf)2Cl(solv)]和[Au(Rf)Cl2(solv)]的混合物（solv = OEt2、OH2）。19F核磁共振和X射线衍射研究使我们能够确定溶液中存在的物种以及溶剂在其形成过程中的作用，而密度泛函理论计算证实了它们演化的热力学基础。根据第四位配体或溶剂的配位强度，发现(μ-Cl)2[顺式 - Au(Rf)2]2或顺式 - [Au(Rf)2ClL]物种（L = OEt2、NCMe、Cl-）的Rf - Rf偶联速率差异很大。
