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

Maximilian Joost; Pauline Gualco; Yannick Coppel; Karinne Miqueu; Christos E Kefalidis; Laurent Maron; Abderrahmane Amgoune; Didier Bourissou

doi:10.1002/anie.201307613

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

Angew Chem Int Ed Engl. 2014 Jan 13;53(3):747-51. doi: 10.1002/anie.201307613. Epub 2013 Dec 4.

Authors

Maximilian Joost¹, Pauline Gualco, Yannick Coppel, Karinne Miqueu, Christos E Kefalidis, Laurent Maron, Abderrahmane Amgoune, 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.

PMID: 24307524
DOI: 10.1002/anie.201307613

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 (31)P and (29)Si 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: NMR spectroscopy; density functional calculations; gold; oxidative additions; silicon.