Direct evidence for intermolecular oxidative addition of sigma(Si-Si) bonds to gold

M. Joost (1) , P. Gualco (1) , Yannick Coppel (2) , Karinne Miqueu (3) , Christos E. Kefalidis (4) , Laurent Maron (4) , A. Amgoune (1) , D. Bourissou (1)

1 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée
2 LCC - Laboratoire de chimie de coordination
3 IPREM - Institut pluridisciplinaire de recherche sur l'environnement et les matériaux
4 LPCNO - Laboratoire de physique et chimie des nano-objets

Oxidative addition plays a major role in transitionmetal 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 P-31 and Si-29 NMR spectroscopy. Their structures (distorted Y shape) and the reaction profile of sigma(Si-Si) bond activation were analyzed by DFT calculations. These results provide evidence for the intermolecular oxidative addition of sigma(Si-Si) bonds to gold and open promising perspectives for the development of new gold-catalyzed redox transformations.

M. Joost, P. Gualco, Yannick Coppel, Karinne Miqueu, Christos E. Kefalidis, et al.. Direct evidence for intermolecular oxidative addition of sigma(Si-Si) bonds to gold. Angewandte Chemie International Edition, 2014, 53 (3), pp.747-751. ⟨10.1002/anie.201307613⟩. ⟨hal-00991874⟩