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Direct Evidence for Intermolecular Oxidative Addition of σ(SiSi) Bonds to Gold
Author(s) -
Joost Maximilian,
Gualco Pauline,
Coppel Yannick,
Miqueu Karinne,
Kefalidis Christos E.,
Maron Laurent,
Amgoune Abderrahmane,
Bourissou Didier
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201307613
Subject(s) - oxidative addition , chemistry , intermolecular force , phosphine , catalysis , transition metal , reductive elimination , redox , oxidative phosphorylation , photochemistry , silylation , inorganic chemistry , molecule , organic chemistry , biochemistry
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 GaCl 3 , 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(SiSi) bond activation were analyzed by DFT calculations. These results provide evidence for the intermolecular oxidative addition of σ(SiSi) bonds to gold and open promising perspectives for the development of new gold‐catalyzed redox transformations.