RhIAr/AuIAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion

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 a...

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Bibliographic Details
Published in:Angewandte Chemie 2019-03, Vol.131 (11), p.3539-3543
Main Authors: Peñas‐Defrutos, Marconi N., Bartolomé, Camino, García‐Melchor, Max, Espinet, Pablo
Format: Article
Language:English
Subjects:
Bimetallische Katalyse
Chemistry
Dichtefunktionalrechnungen
Exchanging
Gold
Insertion
Isomerization
Oxidative Addition
Reaktionsmechanismen
Rhodium
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Summary: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. Transmetallierung mal anders: Eine Kombination kinetischer und theoretischer Studien zeigt, dass der C6F5/C6Cl2F3(Pf/Rf)‐Austausch zwischen [AuPf(AsPh3)] und trans‐[RhRf(CO)(AsPh3)2] nicht durch eine typische konzertierte Pf/Rf‐Transmetallierung erfolgt, sondern vielmehr der nukleophile Angriff von RhI am Goldzentrum eine asymmetrische oxidative Insertion von Rh in die Au‐Aryl‐Bindung auslöst (siehe Schema).
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201813419