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

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 reaction...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2015-04, Vol.137 (16), p.5328-5331
Main Authors: Liberman-Martin, Allegra L, Bergman, Robert G, Tilley, T. Don
Format: Article
Language:English
Subjects:
Aldehydes - chemistry
Catalysis
Catechols - chemistry
Fluorocarbons - chemistry
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Lewis Acids - chemistry
Models, Molecular
Silanes - chemistry
Silicon Compounds - chemistry
Stereoisomerism
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Summary: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 NBu4BArF 4 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.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.5b02807