Water-Mediated Proton Transfer: A Mechanistic Investigation on the Example of the Hydration of Sulfur Oxides

We outline general mechanistic features of “water-mediated proton transfer” in the example of the isomerization reaction in hydrogen-bonded sulfur oxide−water supermolecules containing up to three water molecules. The nucleophilic attack of a water oxygen on the sulfur atom occurs concertedly with the (multiple) proton-transfer event(s). The protons are transferred according to the well-known hydrogen-bond compression mechanism. However, contrary to “pure” multiple proton-transfer reactions, the protons are transferred asynchronously. These mechanistic features force the reaction to be classical rather than quantum-tunneling-dominated down to rather low temperatures. In the quantum-dominated temperature region, tunneling takes place only if all protons tunnel through the barrier. Straight line corner cutting (large curvature tunneling) does not dominate at any temperature, as the reduced mass corresponding to reaction coordinate motion does not drop to values low enough in the reaction barrier region. The asymmetric nature of the potential energy surface even allows different mechanisms involving transient H 3 O + rotation termed “molecular swing” and a H 2 SO 3 isomerization to be favorable compared to water-mediated triple proton transfer in the case of three participating water molecules.