Gold-mediated insertion of oxygen into silicon-silicon bond: An original Au(I)/Au(III) redox sequence

P. Gualco (1) , S. Ladeira , Karinne Miqueu (2) , A. Amgoune (1) , D. Bourissou (1)

1 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée
2 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux

The diphosphine-disilane iPr 2(o-C 6H 4)SiMe 2SiMe 2(o-C 6H 4)PiPr 2 reacts with AuCl(SMe 2) via coordination of the two phosphines and oxidative addition of the σ-Si-Si bond. The ensuing bis(silyl) gold(III) complex has been unequivocally authenticated by NMR spectroscopy at -60 °C. Upon heating, it evolves cleanly to give a disiloxane gold(I) complex that has been fully characterized, including by X-ray diffraction analysis. Oxidation of the disilane proceeds via an original Au(I)/Au(III) redox sequence. According to 18O labeling experiments, both water and dioxygen are competent oxygen sources. Oxidative addition of the σ-Si-Si bond to form a bis(silyl) gold(III) complex seems to be a prerequisite for the disilane → disiloxane conversion to occur. © 2012 American Chemical Society.

Domaines: Catalyse; Chimie de coordination; Chimie organique; Polymères; Chimie théorique et/ou physique

P. Gualco, S. Ladeira, Karinne Miqueu, A. Amgoune, D. Bourissou. Gold-mediated insertion of oxygen into silicon-silicon bond: An original Au(I)/Au(III) redox sequence. Organometallics, 2012, 31 (17), pp.6001-6004. ⟨10.1021/om3006905⟩. ⟨hal-01613237⟩