RT info:eu-repo/semantics/article T1 RhIAr/AuIAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion A1 Peñas de Frutos, Marconi Nicolás A1 Bartolomé Albistegui, María del Camino A1 García Melchor, Max A1 Espinet Rubio, Pablo K1 Gold K1 Oro K1 Bimetallic Catalysis K1 Catálisis bimetálica K1 Functional density calculation K1 Cálculo de densidad funcional K1 Oxidative Addition K1 Adición oxidante K1 Reaction mechanisms K1 Mecanismos de reacción K1 Rhodium K1 Rodio AB By combining kinetic experiments, theoretical calculationsand microkinetic modelling, we show that the Pf/Rf (C6F5/C6Cl2F3)exchange between [AuPf(AsPh3)] and trans-[RhRf(CO)(AsPh3)2]does not occur through the typical concerted Pf/Rf transmetalationvia electron deficient double bridges. Instead, it involves asymmetricoxidative insertion of the RhI complex into the (Ph3As)Au–Pf bondproducing a [(Ph3As)Au–RhPfRf(CO)(AsPh3)2] intermediate, followedby isomerization and reductive elimination of [AuRf(AsPh3)].Interesting differences are found between the LAu–Ar asymmetricoxidative insertion and the classical oxidative addition process of H2to Vaska's complexes. PB Wiley Online Library SN 1521-3757 YR 2019 FD 2019 LK http://uvadoc.uva.es/handle/10324/38350 UL http://uvadoc.uva.es/handle/10324/38350 LA eng NO Angewandte Chemie, 2019, vol. 131, n. 11. p. 3539-3543 NO Producción Científica DS UVaDOC RD 11-dic-2024