A Chromium(III)-Superoxo Complex as a Three-Electron Oxidant with a Large Tunneling Effect in Multi-Electron Oxidation of NADH Analogues.

Metal-superoxo species are involved in a variety of enzymatic oxidation reactions, and multi-electron oxidation of substrates is frequently observed in those enzymatic reactions. A CrIII -superoxo complex, [CrIII (O2 )(TMC)(Cl)]+ (1; TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), is described that acts as a novel three-electron oxidant in the oxidation of dihydronicotinamide adenine dinucleotide (NADH) analogues. In the reactions of 1 with NADH analogues, a CrIV -oxo complex, [CrIV (O)(TMC)(Cl)]+ (2), is formed by a heterolytic O-O bond cleavage of a putative CrII -hydroperoxo complex, [CrII (OOH)(TMC)(Cl)], which is generated by hydride transfer from NADH analogues to 1. The comparison of the reactivity of NADH analogues with 1 and p-chloranil (Cl4 Q) indicates that oxidation of NADH analogues by 1 proceeds by proton-coupled electron transfer with a very large tunneling effect (for example, with a kinetic isotope effect of 470 at 233 K), followed by rapid electron transfer.