Density Functional Modeling of Ligand Effects on Electronic Structure and C–H Bond Activation Activity of Copper(III) Hydroxide Compounds

A series of Cu­(III)–OH complexes supported by differently substituted bis­(carboxamido)­pyridine ligands is modeled to identify factors affecting electronic structure and hydrogen atom transfer reactivity. Activation of hydrocarbon substrates is inferred to be influenced by a combination of many factors, including overall charge state, counterion nature (when present), solvation, attractive and repulsive steric interactions, and quantum mechanical tunneling along the reaction coordinate.