Inspired by the unusual active site structures and reactivities exhibited by copper enzymes, we seek to prepare and characterize synthetic complexes in order to test hypotheses developed to explain the novel functions of the biological sites. Monocopper-hydroxo complexes at high oxidation states are proposed intermediates in oxidation catalysis by copper enzymes and other catalysts, and thus are key targets for synthesis and characterization. Recently, we identified a Cu(III)-OH complex supported by a pyridine(dicarboxamide) ligand,1 and found that it performed hydrogen atom abstraction reactions at high rates. In this lecture, progress toward understanding the basis for these high rates will be presented. Evaluation of the thermondynamics of the process, as well as kinetic and mechanistic features of the reactions of Cu(III)-OH complexes supported by various ligands will be described. 1. (a) Donoghue, P. J.; Tehranchi, J.; Cramer, C. J.; Sarangi, R.; Solomon, E. I.; Tolman, W. B. J. Am. Chem. Soc. 2011, 133, 17602-17605. (b) Dhar, D.; Tolman, W. B. J. Am. Chem. Soc. 2015, 137, 1322-1329.

Thermodynamics and mechanistic insights into C-H bond activation by the Cu(III)-OH core

251st National Meeting (2016)

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