Dissociation of Ionized 1,2-Ethanediol and 1,2-Propanediol: Proton-Transport Catalysis with Electron Transfer †

Ab initio molecular orbital (MO) calculations support the proposal that the key processes in the rearrangement of HOCH2CH2OH•+ and HOCH2CH(CH3)OH•+ (ionized 1,2-ethanediol and 1,2-propanediol) are sequential transfers of a proton and an electron taking place from one partner to the other in ion−dipole complexes rather than prompt hydrogen atom shifts taking place in distonic ions. Although the proposed distonic ions in the alternative mechanism …