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Density Functional Modeling of Ligand Effects on Electronic Structure and C-H Bond Activation Activity of Copper(III)
Büsra Dereli1, Mohammad R Momeni1, Christopher J Cramer1
1Department of Chemistry, Minnesota Supercomputing Institute, and Chemical Theory Center , University of Minnesota , Minneapolis , Minnesota 55455 , United States.
Abstract:
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.
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