Affiliation:
1. CNRS/Université Paul Sabatier Laboratoire Hétérochimie, Fondamentale et Appliquée (LHFA, UMR 5069) 118 route de Narbonne 31062 Toulouse Cedex 09 France
2. CNRS/Université de Pau et des Pays de l'Adour, E2S-UPPA Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux (IPREM, UMR 5254) Hélioparc 2 Avenue du Président Angot 64053 Pau Cedex 09 France
Abstract
AbstractThe coordination of secondary phosphine oxides (SPO) was shown to efficiently promote the activation of C(sp2)−I bonds by gold, as long as a base is added (NEt3, K2CO3). These transformations stand as a new type of chelation‐assisted oxidative addition to gold. The role of the base and the influence of the electronic properties of the P‐ligand were analyzed computationally. Accordingly, the oxidative addition was found to be dominated by Au→(Ar−I) backdonation. In this case, gold behaves similarly to palladium, suggesting that the inverse electron flow reported previously (with prevailing (Ar−I)→Au donation, resulting in faster reactions of electron‐enriched substrates) is a specific feature of electron‐deficient cationic gold(I) complexes. The reaction gives straightforward access to (P=O,C)‐cyclometallated Au(III) complexes. The possibility to chemically derivatize the SPO moiety at Au(III) was substantiated by protonation and silylation reactions.
Funder
Centre National de la Recherche Scientifique
Agence Nationale de la Recherche
European Commission
Université de Toulouse
Subject
General Chemistry,Catalysis,Organic Chemistry