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

Dereli, B.; Momeni, M. R.; Cramer, C. J.
Inorg. Chem. 2018, 57, 9807 (doi:10.1021/acs.inorgchem.8b01530).

A series of Cu(III)-OH complexes supported by differently substituted bis(carboxamido)pyridine ligands is modeled in order to identify factors affecting electronic structure and hydrogen atom transfer (HAT) 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.