Debanjan Dhar , Gereon M. Yee , Andrew D. Spaeth , David W. Boyce , Hongtu Zhang , Büsra Dereli , Christopher J. Cramer * , and William B. Tolman * Department of Chemistry, Center for Metals in Biocatalysis, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota , 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455, United States J. Am. Chem. Soc. , Article ASAP DOI: 10.1021/jacs.5b10985 Publication Date (Web): December 22, 2015 Copyright © 2015 American Chemical Society * cramer@umn.edu , * wtolman@umn.edu Abstract Two new ligand sets, pipMe LH 2 and NO2 LH 2 ( pipMe L = N,N ′ - bis(2,6-diisopropylphenyl)-1-methylpiperidine-2,6-dicarboxamide, NO2 L = N , N ′-bis(2,6-diisopropyl-4-nitrophenyl)pyridine-2,6-dicarboxamide), are reported which are designed to perturb the overall electronics of the copper(III)–hydroxide core and the resulting effects on the thermodynamics and kinetics of its hydrogen-atom abstraction (H...