Electron transfer is ubiquitous in chemistry, and the standard reduction potential is an essential and versatile tool both to characterize molecular properties and offer insights into reaction mechanisms. Copper complexes are widely implicated in the field of biological oxygen chemistry and play an important role in homogeneous and heterogeneous catalysis, particularly with respect to one-electron transfer processes. Considerable attention is thus devoted to elucidating the mechanistic details of copper-based oxidation catalysts and enzymes. However, the prediction of standard reduction potentials in transition-metal chemistry can sometimes be challenging, and density functional theory (DFT) predictions can be extremely sensitive to choice of functional in worst-case scenarios. We focus here on the performance of various density functionals when applied to the redox chemistry of mono-nuclear Cu species relevant to water oxidation catalysis1 and C–H bond activation,2 and other topics. A recently reported oxidation of Cu(III) to Cu(IV) has also been inspected.3 In order to assess the accuracy of computed redox potentials, different computational protocols and a range of DFT functionals have been applied to a set of mono-nuclear Cu systems to identify the impact of shortcomings of DFT such as self-interaction error, and model limitations, such as ion-pairing in low-dielectric solvents. 1. Coggins, M. K.; Zhang, M.-T.; Chen, Z.; Song, N.; Meyer, T. J. Angew. Chem. Int. Ed. 2014, 53, 12226. 2. Dhar, D.; Tolman, W. B. J. Am. Chem. Soc. 2015, 137, 1322. 3. Sinha, W.; Sommer, M. G.; Deibel, N.; Ehret, F.; Bauer, M.; Sarkar, B.; Kar, S. Angew. Chem. Int. Ed. DOI: 10.1002/anie.201507330.

Performance of density functionals for mono-nuclear Cu standard reduction potentials

251st National Meeting (2016)

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