The important physico-chemical property characterizing processes associated with an electron transfer is the reduction potential of the given system(s). At the same time, it also represents one of the important (and direct) links between theoretical calculations and experimental data that may a posteriori verify the plausibility of a particular structural assignment or a reaction scheme. Therefore, reliable computational protocols and experience in calculations of reduction potentials are highly desirable. In this contribution, our recent efforts to come up with accurate values of reduction potentials will be summarized and caveats in the treatment of two important terms involved in their calculations (solvation energies and in vacuo electron affinities/ionization energies) highlighted. The presented examples will include octahedral complexes of ruthenium(II) and osmium (II),[1,2,3] several aromatic systems [4,5] computational and electrochemical study of ferrocene derivatives [6], and our initial efforts to evaluate the reduction potentials of metal ions in the two enzymes: multi-copper oxidases [7] and manganese superoxide dismutases [8]. [1] Vrábel, M. et al. Eur. J. Inorg. Chem. 2007, 1752. [2] Srnec, M.; et al. J. Am. Chem. Soc. 2008, 130, 10947. [3] Rulíšek, L. J. Phys. Chem. C 2013, 117, 16871. [4] Chua, C. K.; Pumera, M.; Rulíšek, L. J. Phys. Chem. C 2012, 116, 4243. [5] Akdag, A. et al. J. Org. Chem. 2015, 80, 80‑89. [6] Khobragade, D. A.; et al. Chem. Eur. J. 2012, 18, 12267. [7] Hu, L. H. et al. U. J. Phys. Chem. B 2011, 115, 13111. [8] Heimdal, J. et al. ChemPhysChem 2011, 12, 3337.

Computational electrochemistry: From small molecules to metalloproteins

250th National Meeting (2015)

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