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Peñas de Frutos, Marconi Nicolás Bartolomé Albistegui, María del Camino García Melchor, Max Espinet Rubio, Pablo 2021-02-25T09:47:20Z 2021-02-25T09:47:20Z 2019 Angewandte Chemie International Edition, 2019, 58,3501 –3505 1433-7851 http://uvadoc.uva.es/handle/10324/45392 10.1002/anie.201813419 3501 11 3505 Angewandte Chemie International Edition 58 Producción Científica 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. Ministerio de Economía, Industria y Competitividad (Projects CTQ2016-80913-P and CTQ2017-89217-P) Junta de Castilla y León (Projects VA051P17, VA062G18 and UIC176) application/pdf eng Wiley info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ © 2019 Wiley Attribution-NonCommercial-NoDerivatives 4.0 Internacional Catálisis bimetálica Bimetallic catalysis 2210 Química Física RhIAr/AuIAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201813419 SI