Reaction Mechanism of Hydroxyl Anion with Benzene

Abstract

The reaction mechanism of hydroxyl anion and benzene has been theoretically studied at the G3MP2B3 level of theory. All possible thermodynamic product channels are considered and investigated. The [C6H6…OH]- complex formation has been found on the most favorable reaction pathway, which is consistent with the previous experimental studies. The proton transfer and hydrogen replacement pathways are endothermic and difficult to occur in the case of the lower experimental collision energy. Additionally, the H2 formation as an exothermal product channel of this reaction system by -119.5 kJ·mol-1 hardly happens because of a high energy barrier. The proton transfer processes of hydroxyl anion, oxygen anion, and fluorine anion from benzene have been compared in the present computation, and the electron transfers in these processes were investigated by the Mulliken charge population analysis as well. Furthermore, the reaction mechanism between hydroxyl anion or hydroxyl radical and benzene, has been also compared and analyzed.