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