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Analyzing the Photo-oxidation of 2-propanol at Indoor Air Level Concentrations Using Field Asymmetric Ion Mobility Spectrometry
Published on: June 14, 2018
Quantum chemical investigation of mechanisms of silane oxidation
1Department of Chemistry, Grinnell College, Grinnell, Iowa 50112, USA. mader_mary@lilly.com
Abstract:
Several mechanisms for the peroxide oxidation of organosilanes to alcohols are compared by quantum chemical calculations, including solvation with the PCM method. Without doubt, the reaction proceeds via anionic, pentacoordinate silicate species, but a profound difference is found between in vacuo and solvated reaction profiles, as expected. In the solvents investigated (CH(2)Cl(2) and MeOH), the most favorable mechanism is addition of peroxide anion to a fluorosilane (starting material or formed in situ), followed by a concerted migration and dissociation of hydroxide anion. In the gas phase, and possibly in very nonpolar solvents, concerted addition-migration of H(2)O(2) to a pentacoordinate fluorosilicate is also plausible.
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