Perturbing the Copper(III)-Hydroxide Unit Through Ligand Structural Variation

Dhar, D.; Yee, G. M.; Spaeth, A. D.; Boyce, D. W.; Zhang, H.; Dereli, B.; Cramer, C. J.; Tolman, W. B.
J. Am Chem. Soc. 2016, 138, 356 (doi:10.1021/jacs.5b10985).

Two new ligand sets, ^pipMeLH₂ and ^NO2LH₂ (^pipMeL = N,N'-bis(2,6-diisopropylphenyl)-1-methylpiperidine-2,6-dicarboxamide, ^NO2L = N,N'-bis(2,6-diisopropyl-4-nitrophenyl)pyridine-2,6-dicarboxamide), are reported which are designed to perturb the overall electronics of the copper(III)-hydroxide core and the resulting effects on the thermodynamics and kinetics of its hydrogen atom abstraction (HAT) reactions. Bond dissociation energies (BDEs) for the O-H bonds of the corresponding Cu(II)-OH₂ complexes were measured that reveal that changes in the redox potential for the Cu(III)/Cu(II) couple are only partially offset by opposite changes in the pK_a, leading to modest differences in BDE among the three compounds. The effects of these changes were further probed by evaluating the rates of HAT by the corresponding Cu(III)-hydroxide complexes from substrates with C-H bonds of variable strength. These studies revealed an overarching linear trend in the relationship between the logk (where k is the second order rate constant) and BDE of the C-H bond broken. Additional subtleties in measured rates arise, however, that are associated with variations in hydrogen-atom abstraction barrier heights and tunneling efficiencies over the temperature range –80 to –20° C, as inferred from measured kinetic isotope effects and corresponding electronic-structure-based transition-state theory calculations.