On the possibility of single-electron transfer during alkaline hydrolysis of sulfophthalides

Abstract

The previously observed generation of radical products during the alkaline hydrolysis of diphenylsulfophthalide (DPSP) and polydiphenylenesulfophthalide in dimethyl sulfoxide (DMSO) is indicative of the involvement of single-electron transfer (SET) in thses processes. The possibility of SET from the hydroxide ion (HI) to the sulfophthalide molecule is determined by the ratio between the ionization potential (IP) of the HI and electron affinity (EA) of the sulfophthalide. According to B3LYP/6-311+G(d,p) calculations for DPSP, EA ver = 0.06 eV and EA ad = 0.58 eV, whereas EA eff = 2.13 eV (with consideration of the C-O bond rupture in the sulfophthalide cycle). Such a value of the electron affinity cannot ensure SET from the HI, the ionization potential of which in DMSO reaches ∼5.25 eV. The EA of the carbocation formed from DPSP is 6.44 eV as calculated in the same approximation. A mode of SET from the HI to the carbocation intermediate formed during DPSP heterolysis in DMSO is proposed. Two possible modifications of the electron donor are considered. The possibility of occurrence of SET from the dimsyl ion and HI-DMSO complex is evaluated using the G3B3 method. The ionization potential of the dimsyl ion in DMSO is almost 1 eV lower than the IP of the HI, which makes the former a preferential donor in comparison with the HI. The ionization potential of the weak HI-DMSO complex even exceeds the IP of the HI; i.e., complexation does not improve the electron-donor properties of the hydroxide ion.