Peñas-Defrutos Marconi N, Bartolomé Camino, García-Melchor Max, Espinet Pablo
IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47071, Valladolid, Spain.
School of Chemistry, Trinity College Dublin, College Green, Dublin 2, Ireland.
Angew Chem Int Ed Engl. 2019 Mar 11;58(11):3501-3505. doi: 10.1002/anie.201813419. Epub 2019 Feb 7.
By combining kinetic experiments, theoretical calculations, and microkinetic modeling, we show that Pf/Rf (C F /C Cl F ) exchange between [AuPf(AsPh )] and trans-[RhRf(CO)(AsPh ) ] does not occur by typical concerted Pf/Rf transmetalation via electron-deficient double bridges. Instead, it involves asymmetric oxidative insertion of the Rh complex into the (Ph As)Au-Pf bond to produce a [(Ph As)Au-RhPfRf(CO)(AsPh ) ] intermediate, followed by isomerization and reductive elimination of [AuRf(AsPh )]. Interesting differences were found between the LAu-Ar asymmetric oxidative insertion and the classical oxidative addition process of H to Vaska complexes.
通过结合动力学实验、理论计算和微观动力学建模，我们表明，[AuPf(AsPh₃)]与反式-[RhRf(CO)(AsPh₃)₂]之间的Pf/Rf（CF/CClF）交换并非通过缺电子双桥的典型协同Pf/Rf金属转移反应发生。相反，它涉及Rh配合物不对称氧化插入到(Ph₃As)Au-Pf键中，生成[(Ph₃As)Au-RhPfRf(CO)(AsPh₃)₂]中间体，随后异构化并还原消除[AuRf(AsPh₃)]。在LAu-Ar不对称氧化插入与H对Vaska配合物的经典氧化加成过程之间发现了有趣的差异。
