B. Chiavarino, M. Crestoni, J. Lemaire
Aug 16, 2013
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Journal
The Journal of chemical physics
Abstract
β-trimethylsilyl-2-propyl cation has been formed by the gas phase protonation of allyl-trimethylsilane and characterized by infrared multiple photon dissociation spectroscopy. The experimental Cβ-Cα (+) stretching feature at 1586 cm(-1), remarkably blue-shifted with respect to a C-C single bond stretching mode, is indicative of high double bond character, a signature of β-stabilizing effect due to hyperconjugation of the trimethylsilyl group in the β-position with respect to the positively charged carbon. Density functional theory calculations at the B3LYP∕6-311++G(2df,2p) level yield the optimized geometries and IR spectra for candidate isomeric cations and for neutral and charged reference species.