RhIAr/AuIAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion

By combining kinetic experiments, theoretical calculations, and microkinetic modeling, we show that Pf/Rf (C₆F₅/C₆Cl₂F₃) exchange between AuPf(AsPh₃)] and trans‐RhRf(CO)(AsPh₃)₂] does not occur by typical concerted Pf/Rf transmetalation via electron‐deficient double bridges. Instead, it involves asymmetric oxidative insertion of the Rh^I complex into the (Ph₃As)Au?Pf bond to produce a (Ph₃As)Au?RhPfRf(CO)(AsPh₃)₂] intermediate, followed by isomerization and reductive elimination of AuRf(AsPh₃)]. Interesting differences were found between the LAu?Ar asymmetric oxidative insertion and the classical oxidative addition process of H₂ to Vaska complexes.