Lewis Acidity of Bis(perfluorocatecholato)silane: Aldehyde Hydrosilylation Catalyzed by a Neutral Silicon Compound

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Bis(perfluorocatecholato)silane Si(catF)2 was prepared, and stoichiometric binding to Lewis bases was demonstrated with fluoride, triethylphosphine oxide, and N,N′-diisopropylbenzamide. The potent Lewis acidity of Si(catF)2 was suggested from catalytic hydrosilylation and silylcyanation reactions with aldehydes. Mechanistic studies of hydrosilylation using an optically active silane substrate, R-(+)-methyl-(1-naphthyl)phenylsilane, proceeded with predominant stereochemical retention at silicon, consistent with a carbonyl activation pathway. The enantiospecificity was dependent on solvent and salt effects, with increasing solvent polarity or addition of NBu4BArF4 leading to a diminished enantiomeric ratio. The medium effects are consistent with an ionic mechanism, wherein hydride transfer occurs prior to silicon–oxygen bond formation.


This is a pre-copy-editing, author-produced PDF of an article accepted for publication in Journal of the American Chemical Society, volume 137, in 2015 following peer review. The definitive publisher-authenticated version is available online at https://doi.org/10.1021/jacs.5b02807.


American Chemical Society