Competing Reaction Pathways in Gas-Phase Oxidation of C₆H₆ by Protonated H₂O₂

Reactions between protonated hydrogen peroxide and benzene (and benzene-<i>d</i>₆) have been studied in the gas phase using an FT-ICR mass spectrometer. Four competing paths for the bimolecular system were identified, namely, proton transfer, hydride abstraction, dissociative single-electron transfer, and an electrophilic addition of HO⁺ to give the Wheland intermediate [C₆H₆, OH]⁺ followed by a subsequent elimination of water. The three latter pathways correspond to three different ways to oxidize benzene. All reaction mechanisms have been modeled using quantum chemical methods, and the calculations are in agreement with the experimental observations. The total reaction rate proceeds at collision rate (slightly higher than the calculated Langevin capture rate), which exemplifies the high reactivity of H₃O₂⁺ toward arenes. These observations demonstrate a much richer chemical landscape than previously inferred from the corresponding condensed phase reaction, where only electrophilic substitution by solvated HO⁺ was described.