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Rh I Ar/Au I Ar′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion
Author(s) -
PeñasDefrutos Marconi N.,
Bartolomé Camino,
GarcíaMelchor Max,
Espinet Pablo
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201813419
Subject(s) - transmetalation , chemistry , reductive elimination , isomerization , oxidative addition , oxidative phosphorylation , crystallography , stereochemistry , photochemistry , catalysis , organic chemistry , biochemistry
By combining kinetic experiments, theoretical calculations, and microkinetic modeling, we show that Pf/Rf (C 6 F 5 /C 6 Cl 2 F 3 ) exchange between [AuPf(AsPh 3 )] and trans ‐[RhRf(CO)(AsPh 3 ) 2 ] does not occur by typical concerted Pf/Rf transmetalation via electron‐deficient double bridges. Instead, it involves asymmetric oxidative insertion of the Rh I complex into the (Ph 3 As)Au−Pf bond to produce a [(Ph 3 As)Au−RhPfRf(CO)(AsPh 3 ) 2 ] intermediate, followed by isomerization and reductive elimination of [AuRf(AsPh 3 )]. Interesting differences were found between the LAu−Ar asymmetric oxidative insertion and the classical oxidative addition process of H 2 to Vaska complexes.