Electron Transfer to Sulfides and Disulfides: Intrinsic Barriers and Relationship between Heterogeneous and Homogeneous Electron-Transfer Kinetics

The electron‐acceptor properties of series of related sulfides and disulfides were investigated in N,N‐dimethylformamide with homogeneous (redox catalysis) and/or heterogeneous (cyclic voltammetry and convolution analysis) electrochemical techniques. The electron‐transfer rate constants were determined as a function of the reaction free energy and the corresponding intrinsic barriers were determined. The dependence of relevant thermodynamic and kinetic parameters on substituents was assessed. The kinetic data were also analyzed in relation to corresponding data pertaining to reduction of diaryl disulfides. All investigated reductions take place by stepwise dissociative electron transfer (DET) which causes cleavage of the CalkylS or SS bond. A generalized picture of how the intrinsic electron‐transfer barrier depends on molecular features, ring substituents, and the presence of spacers between the frangible bond and aromatic groups was established. The reduction mechanism was found to undergo a progressive (and now predictable) transition between common stepwise DET and DET proceeding through formation of loose radical anions. The intrinsic barriers were compared with available results for ET to several classes of dissociative‐ and nondissociative‐type acceptors, and this led to verification that the heterogeneous and the homogeneous data correlate as predicted by the Hush theory. Dissociative reduction of series of sulfides and disulfides was investigated, and a generalized picture of how the intrinsic electron‐transfer barrier depends on various molecular features could be established. The heterogeneous and the homogeneous intrinsic barriers were compared with results for electron transfer to a variety of classes of dissociative‐ and nondissociative‐type acceptors (see picture), and the validity of the Hush model could be verified.