Quantum chemical investigation of mechanisms of silane oxidation

Mary M. Mader, Per-Ola Norrby

Research output: Contribution to journalJournal articleResearchpeer-review


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 (CH2Cl2 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 H2O2 to a pentacoordinate fluorosilicate is also plausible.
Original languageEnglish
JournalJournal of the American Chemical Society
Issue number9
Pages (from-to)1970-1976
Publication statusPublished - 2001


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