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Direct Evidence for Intermolecular Oxidative Addition of σ(SiSi) Bonds to Gold |
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| Authors: | Maximilian Joost Dr. Pauline Gualco Dr. Yannick Coppel Dr. Karinne Miqueu Dr. Christos E. Kefalidis Dr. Laurent Maron Dr. Abderrahmane Amgoune Dr. Didier Bourissou |
| Affiliation: | 1. Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier/CNRS UMR 5069, 118 Route de Narbonne, 31062 Toulouse Cedex 09 (France) http://hfa.ups‐tlse.fr/LBPB/index_lbpb.htm;2. Laboratoire de Chimie de Coordination, CNRS UPR 8241, 205 Route de Narbonne, 31077 Toulouse (France);3. Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux, Equipe Chimie Physique, Université de Pau et des Pays de l'Adour/CNRS UMR 5254, Hélioparc, 2 Avenue du Président Angot, 64053 Pau cedex 09 (France);4. Laboratoire de Physique et Chimie des Nano‐Objets, Université de Toulouse, INSA, UPS, LPCNO, Université de Toulouse/CNRS UMR 5215/INSA, 135 Avenue de Rangueil, 31077 Toulouse (France) |
| Abstract: | Oxidative addition plays a major role in transition‐metal catalysis, but this elementary step remains very elusive in gold chemistry. It is now revealed that in the presence of GaCl3, phosphine gold chlorides promote the oxidative addition of disilanes at low temperature. The ensuing bis(silyl) gold(III) complexes were characterized by quantitative 31P and 29Si NMR spectroscopy. Their structures (distorted Y shape) and the reaction profile of σ(Si? Si) bond activation were analyzed by DFT calculations. These results provide evidence for the intermolecular oxidative addition of σ(Si? Si) bonds to gold and open promising perspectives for the development of new gold‐catalyzed redox transformations. |
| Keywords: | density functional calculations gold NMR spectroscopy oxidative additions silicon |