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.