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- Title
Rh<sup>I</sup>Ar/Au<sup>I</sup>Ar′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion.
- Authors
Peñas‐Defrutos, Marconi N.; Bartolomé, Camino; García‐Melchor, Max; Espinet, Pablo
- Abstract
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.
- Subjects
METALATION; CHEMICAL kinetics; CHEMICAL bonds; INTERMEDIATES (Chemistry); ELIMINATION reactions
- Publication
Angewandte Chemie, 2019, Vol 131, Issue 11, p3539
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201813419