Homolytic cleavage of peroxide bonds via a single electron transfer of a frustrated Lewis pair

Abstract

Single electron transfer (SET) reactions are effected by the combination of a Mes₃P/B(C₆F₅)₃ frustrated Lewis pair with benzoyl peroxide derivatives. The resulting homolytic cleavage of the peroxide bonds affords the radical salts [Mes₃P˙]⁺[RCOOB(C₆F₅)₃]⁻ (R = Ph 1, p-BrC₆H₄2, p-MeC₆H₄3). These species react with Ph₃SnH to give [Mes₃PH]⁺[RCOOB(C₆F₅)₃]⁻ (R = Ph 10, p-BrC₆H₄11, p-MeC₆H₄12) and (Ph₃Sn)₂. The mechanism of these SET reactions is discussed in light of control experiments and DFT calculations.