Neutral Phenolic Contaminants Are Not Necessarily More Resistant to Permanganate Oxidation Than Their Dissociated Counterparts: Importance of Proton-Coupled Electron Transfer

Despite decades of research on phenols oxidation by permanganate, there are still considerable uncertainties regarding the mechanisms accounting for the unexpected parabolic pH-dependent oxidation rate. Herein, the pH effect on phenols oxidation was reinvestigated experimentally and theoretically by highlighting the previously unappreciated proton transfer. The results revealed that the oxidation of protonated phenols occurred via proton-coupled electron transfer (PCET) pathways, which can switch from ETPT (electron transfer followed by proton transfer) to CEPT (concerted electron-proton transfer) or PTET (proton transfer followed by electron transfer) with an increase in pH. A PCET-based model was thus established, and it could fit the kinetic data of phenols oxidation by permanganate well. In contrast with what was previously thought, both the simulating results and the density functional theory calculation indicated the rate of CEPT reaction of protonated phenols with OH- as the proton acceptor was much higher than that of deprotonated phenols, which could account for the pH-rate profiles for phenols oxidation. Analysis of the quantitative structure-activity relationships among the modeled rate constants, Hammett constants, and pKa values of phenols further supports the idea that the oxidation of protonated phenols is dominated by PCET. This study improves our understanding of permanganate oxidation and suggests a new pattern of reactivity that may be applicable to other systems.