Reactivity of the copper(III)-hydroxide unit with phenols

Kinetic studies of the reactions of two previously characterized copper((III))-hydroxide complexes (LCuOH and (LCuOH)-L-NO2, where L = N, N'-bis(2,6-diisopropylphenyl)-2,6-pyridine-dicarboxamide and L-NO2 = N, N'-bis(2,6-diisopropyl-4-nitrophenyl) pyridine-2,6-dicarboxamide) with a series of para substituted phenols ((ArOH)-Ar-X where X = NMe2, OMe, Me, H, Cl, NO2, or CF3) were performed using low temperature stopped-flow UV-vis spectroscopy. Second-order rate constants (k) were determined from pseudo first-order and stoichiometric experiments, and follow the trends CF3 < NO2 < Cl < H < Me < OMe < NMe2 and LCuOH < NO2LCuOH. The data support a concerted proton-electron transfer (CPET) mechanism for all but the most acidic phenols (X = NO2 and CF3), for which a more complicated mechanism is proposed. For the case of the reactions between (ArOH)-Ar-NO2 and LCuOH in particular, competition between a CPET pathway and one involving initial proton transfer followed by electron transfer (PT/ET) is supported by multiwavelength global analysis of the kinetic data, formation of the phenoxide (ArO-)-Ar-NO2 as a reaction product, observation of an intermediate [LCu(OH2)](+) species derived from proton transfer from NO2ArOH to LCuOH, and thermodynamic arguments indicating that initial PT should be competitive with CPET.