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 Catálisis bimetálica
K1 Bimetallic catalysis
K1 2210 Química Física
AB 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.
PB Wiley
SN 1433-7851
YR 2019
FD 2019
LK http://uvadoc.uva.es/handle/10324/45392
UL http://uvadoc.uva.es/handle/10324/45392
LA eng
NO Angewandte Chemie International Edition, 2019, 58,3501 –3505
NO Producción Científica
DS UVaDOC
RD 11-jul-2024