Theoretical study on hydrogen transfer in the dissociation of dimethyl disulfide radical cations

Hydrogen transfer (HT) is of crucial importance in biochemistry and atmospheric chemistry. Here, HT processes involved in the dissociation reaction of dimethyl disulfide radical cations (DMDS+, CH3SSCH3+) are investigated using quantum chemical calculations. Four HTs from the C to S atom and one HT from the S to S atom are observed and the most probable paths are proposed in the dissociation channel from DMDS+ to CHnS+ (n = 2-4). The mechanisms of all these five HTs are described as hydrogen atom transfer (HAT) and four of them are accompanied by electron transfer (ET). Considering the catalytic effect of water molecules existing in organisms and the atmosphere, five HT processes in the dissociation of the [DMDS + H2O](+) complex are further explored, which show lower free energy barriers. With the participation of water molecules acting as a base, two HTs from the C to the S atom, which have the largest decrease in energy barriers, are characterized as concerted proton-coupled electron transfer (cPCET). These results can be extended to understand the mechanism of the HT process during the dissociation of disulfide and help provide a strategy to design a rare cPCET mechanism for the activation of the C-H bond.