Mechanistic Dichotomy in Proton-Coupled Electron-Transfer Reactions of Phenols with a Copper Superoxide Complex

The kinetics and mechanism(s) of the reactions of [K(Krypt)][LCuO₂] (Krypt = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, L = a bis(arylcarboxamido)pyridine ligand) with 2,2,6,6-tetramethylpiperdine- N-hydroxide (TEMPOH) and the para-substituted phenols ^XArOH (X = para substituent NO₂, CF₃, Cl, H, Me, ^tBu, OMe, or NMe₂) at low temperatures were studied. The reaction with TEMPOH occurs rapidly ( k = 35.4 ± 0.3 M^-1 s^-1) by second-order kinetics to yield TEMPO^• and [LCuOOH]^- on the basis of electron paramagnetic resonance spectroscopy, the production of H₂O₂ upon treatment with protic acid, and independent preparation from reaction of [NBu₄][LCuOH] with H₂O₂ ( K_eq = 0.022 ± 0.007 for the reverse reaction). The reactions with ^XArOH also follow second-order kinetics, and analysis of the variation of the k values as a function of phenol properties (Hammett σ parameter, O-H bond dissociation free energy, p K_a, E_1/2) revealed a change in mechanism across the series, from proton transfer/electron transfer for X = NO₂, CF₃, Cl to concerted-proton/electron transfer (or hydrogen-atom transfer) for X = OMe, NMe₂ (data for X = H, Me, ^tBu are intermediate between the extremes). Thermodynamic analysis and comparisons to previous results for LCuOH, a different copper-oxygen intermediate with the same supporting ligand, and literature for other [CuO₂]⁺ complexes reveal significant differences in proton-coupled electron-transfer mechanisms that have implications for understanding oxidation catalysis by copper-containing enzymes and abiological catalysts.