Investigating the reactivity of radical cations: experimental and computational insights into the reactions of radical cations with alcohol and p-toluene sulfonamide nucleophiles.

The reactivity of electrochemically generated radical cations toward alcohol and p-toluene sulfonamide nucleophiles was directly investigated through competition experiments. Alcohol-trapping of the radical cation is the kinetically favored pathway and is reversible. Trapping with the sulfonamide leads to the thermodynamic product. Both reaction pathways were investigated computationally with density functional theory (UB3LYP/6-31G(d)) calculations.