210362-80-4Relevant academic research and scientific papers
Oxidative Desilylation of Alkylsilanes with Triphenylcarbenium Ion. Control of Transition-State Geometry
Washburne, Stephen S.,Szendroi, Robert
, p. 691 - 693 (2007/10/02)
Ten acylic, cyclic, and aralkyl-type silanes were treated with triphenylcarbenium tetrafluoroborate in dichloromethane to measure rates of oxidative desilylation: RCH2CH2SiR3+Ph3C(1+)BF4(1-)->Ph3CH+RCH=CH2+R3SiF+BF3.The divergence of rates, from Ph2CHCH2SiMe3, which was inert, through dimethylsilacyclopentane (k2=4E-6), to dimethylsilacyclohexane (k2=2.2E-3), can not be rationalized on purely electronic grounds.A transition state requiring anticoplanar arrangement of the silicon moiety and β-hydrogen to be extruded is proposed.Dimethylsilacyclobutane, which reacts extremely rapidly (k2 approx. 2E-2), suffers allylic cleavage of the initially formed fluoro(2-propenyl)dimethylsilane.As the olefin products suffer decomposition or polymerization under the reaction conditions, this desilylation is of minimal preparative value.
Gas-Phase Reactions of Anions with Substituted Silanes
DePuy, C. H.,Bierbaum, Veronica M.,Flippin, L. A.,Grabowski, Josef J.,King, Gary K.,et al.
, p. 5012 - 5015 (2007/10/02)
The gas-phase reactions of fluoride, amide, hydroxide, and methoxide ions with a variety of substituted silanes have been studied by the flowing afterglow technique.Fluoride reacts readily with trimethylsilyl derivatives to displace benzyl, alkenyl, and alkynyl anions.These reactions have also been used to generate specific structural isomers (CH3CC- and CH2C=C=CH-).Anions more basic than phenide ion cannot be produced in this manner, and their parent trimethylsilanes interact with fluoride by more complex mechanisms.Amide, hydroxide, and methoxide ions react with substituted trimethylsilanes by both displacement and proton abstraction whenever an acidic hydrogen is present; in the absence of displaceable groups and acidic hydrogen, the reactions of amide, hydroxide, and methoxide parallel those of fluoride ion.
