RhIAr/AuIAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion |
| |
Authors: | Marconi N. Pe as‐Defrutos,Camino Bartolom ,Max Garcí a‐Melchor,Pablo Espinet |
| |
Affiliation: | Marconi N. Peñas‐Defrutos,Camino Bartolomé,Max García‐Melchor,Pablo Espinet |
| |
Abstract: | 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 RhI 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. |
| |
Keywords: | Bimetallische Katalyse Dichtefunktionalrechnungen Gold Oxidative Addition Reaktionsmechanismen Rhodium |
|
|