Kinetic studies of the reactions of two previously characterized copper(iii)-hydroxide complexes (LCuOH and NO2LCuOH, where L = N,N′-bis(2,6-diisopropylphenyl)-2,6-pyridine-dicarboxamide and NO2L = N,N′-bis(2,6-diisopropyl-4-nitrophenyl)pyridine-2,6-dicarboxamide) with a series of para substituted phenols (XArOH 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 NO2ArOH 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 NO2ArO- 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.
Bibliographical noteFunding Information:
We thank the NIH (grant R37GM47365 to W. B. T. and grant 5R01GM050422 to J. M. M.) for financial support. We acknowledge Dr Bradley McKeown for his help with the stopped-flow measurements. X-ray diffraction experiments were performed using a crystal diffractometer acquired through NSF-MRI Award CHE-1229400.