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RhIAr/AuIAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion Peñas de Frutos, Marconi Nicolás Bartolomé Albistegui, María del Camino García Melchor, Max Espinet Rubio, Pablo Catálisis bimetálica Bimetallic catalysis 2210 Química Física 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) 2021-02-25T09:47:20Z 2021-02-25T09:47:20Z 2019 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion 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 eng https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201813419 Attribution-NonCommercial-NoDerivatives 4.0 Internacional info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ © 2019 Wiley application/pdf Wiley https://uvadoc.uva.es/bitstream/10324/45392/4/Angewandte2019.pdf.jpg Hispana TEXT http://creativecommons.org/licenses/by-nc-nd/4.0/ UVaDOC. Repositorio Documental de la Universidad de Valladolid http://uvadoc.uva.es/handle/10324/45392