Role of protons in superoxide reduction by a superoxide reductase analogue

Superoxide reduction by thiolate-ligated FeII(SMe2N4(tren))]+ (1) involves two proton-dependent steps and a single peroxide intermediate, FeIII(SMe2N4(tren))(OOH)]+ (2). An external proton donor is required, ruling out mechanisms involving H+ or H-atom abstraction from the ligand N-H. The initial protonation step affording 2 occurs with fairly basic proton donors (EtOH, MeOH, NH4+) in THF. More acidic proton donors are required to cleave the Fe-O(peroxide) bond in MeOH, and this occurs via a dissociative mechanism. Reaction rates are dependent on the pKa of the proton donor, and a common FeIII(SMe2N4(tren))(MeOH)]2+ (3) intermediate is involved. Acetic acid releases H2O2 from 2 under pseudo-first-order conditions (HOAc] = 138 mM, 2] = 0.49 mM) with a rate constant of 8.2 x 10(-4) s(-1) at -78 degrees C in MeOH. Reduction of 3 with Cp2Co regenerates the active catalyst 1.