title: The role of the HOOO(-) anion in the ozonation of alcohols: large differences in the gas-phase and in the solution-phase mechanism.
abstract: The mechanism of the ozonation of isopropyl alcohol was investigated for the gas and the solution phase using second-order many body perturbation theory and density functional theory (DFT) with the hybrid functional B3LYP and a 6-311++G(3df,3pd) basis set. A careful analysis of calculated energies (considering thermochemical corrections, solvation energies, BSSE corrections, the self-interaction error of DFT, etc.) reveals that the gas-phase mechanism of the reaction is dominated by radical or biradical intermediates while the solution-phase mechanism is characterized by hydride transfer and the formation of an intermediate ion pair that includes the HOOO(-) anion. The product distribution observed for the ozonation in acetone solution can be explained on the basis of the properties of the HOOO(-) anion. General conclusions for the ozonation of alcohols and the toxicity of ozone (inhaled or administered into the blood) can be drawn.
authors.affiliation: Department of Theoretical Chemistry, Göteborg University, Reutersgatan 2, S-413 20 Göteborg, Sweden.
authors.forename: Anan
authors.initials: A
authors.lastname: Wu
authors.forename: Dieter
authors.initials: D
authors.lastname: Cremer
authors.forename: Bozo
authors.initials: B
authors.lastname: Plesnicar