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oai:uvadoc.uva.es:10324/453922021-06-24T07:44:23Zcom_10324_28542com_10324_952com_10324_894col_10324_28543

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 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. 2021-02-25T09:47:20Z 2021-02-25T09:47:20Z 2021-02-25T09:47:20Z 2019 info:eu-repo/semantics/article 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 info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ © 2019 Wiley Attribution-NonCommercial-NoDerivatives 4.0 Internacional Wiley