Effects of Charged Ligand Substituents on the Properties of the Formally Copper(III)-Hydroxide ([CuOH]2+) Unit.

Abstract

With the goal of understanding how distal charge influences the properties and hydrogen atom transfer (HAT) reactivity of the [CuOH]2+ core proposed to be important in oxidation catalysis, the complexes [M]3[SO3LCuOH] (M = [K(18-crown-6)]+ or [K(crypt-222)]+) and [NMe3LCuOH]X (X = BArF4- or ClO4-) were prepared, in which SO3- or NMe3+ substituents occupy the para positions of the flanking aryl rings of the supporting bis(carboxamide)pyridine ligands. Structural and spectroscopic characterization showed that the [CuOH]+ cores in the corresponding complexes were similar, but cyclic voltammetry revealed the E1/2 value for the [CuOH]2+/[CuOH]+ couple to be nearly 0.3 V more oxidizing for the [NMe3LCuOH]2+ than the [SO3LCuOH]- species, with the latter influenced by interactions between the distal -SO3- substituents and K+ or Na+ counterions. Chemical oxidations of the complexes generated the corresponding [CuOH]2+ species as evinced by UV-vis spectroscopy. The rates of HAT reactions of these species with 9,10-dihydroanthracene to yield the corresponding [Cu(OH2)]2+ complexes and anthracene were measured, and the thermodynamics of the processes were evaluated via determination of the bond dissociation enthalpies (BDEs) of the product O-H bonds. The HAT rate for [SO3LCuOH]- was found to be ∼150 times faster than that for [NMe3LCuOH]2+, despite finding approximately the same BDEs for the product O-H bonds. Rationales for these observations and new insights into the roles of supporting ligand attributes on the properties of the [CuOH]2+ unit are presented.