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 19-abr-2024