Quantum-chemical predictions of redox potentials of organic anions in dimethyl sulfoxide and reevaluation of bond dissociation enthalpies measured by the electrochemical methods

The Journal of Physical Chemistry. a
Yao FuQing-Xiang Guo

Abstract

A first-principle theoretical protocol was developed that could predict the absolute pK(a) values of over 250 structurally unrelated compounds in DMSO with a precision of 1.4 pK(a) units. On this basis we developed the first theoretical protocol that could predict the standard redox potentials of over 250 structurally unrelated organic anions in DMSO with a precision of 0.11 V. Using the two new protocols we systematically reevaluated the bond dissociation enthalpies (BDEs) measured previously by the electrochemical methods. It was confirmed that for most compounds the empirical equation (BDE = 1.37 pK(HA) + 23.1E(o) + constant) was valid. The constant in this equation was determined to be 74.0 kcal/mol, compared to 73.3 kcal/mol previously reported. Nevertheless, for a few compounds the empirical equation could not be used because the solvation energy changed dramatically during the bond cleavage, which resulted from the extraordinary change of dipole moment during the reaction. In addition, we found 40 compounds (mostly oximes and amides) for which the experimental values were questionable by over 5 kcal/mol. Further analyses revealed that all these questionable BDEs could be explained by one of the three following reasons: (...Continue Reading

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Citations

Mar 26, 2014·Journal of Molecular Modeling·Jochen HeilStefan M Kast
Nov 13, 2007·Biophysical Chemistry·Mansoor NamazianMichelle L Coote
Mar 11, 2010·Biochimica Et Biophysica Acta·Vivek SharmaVille R I Kaila
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Mar 3, 2011·Chemistry, an Asian Journal·Chen WangYao Fu
Sep 7, 2016·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Joaquín CalboJuan Aragó
Mar 12, 2009·The Journal of Organic Chemistry·Feizhi DingHaobin Wang
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Sep 14, 2010·Journal of Chemical Theory and Computation·Mansoor NamazianMichelle L Coote
May 27, 2011·The Journal of Physical Chemistry. a·Aleksander TrummalIlmar A Koppel
Apr 22, 2020·The Journal of Physical Chemistry. a·Haishan YuJun Jiang
Oct 16, 2007·Journal of the American Chemical Society·Yao FuQing-Xiang Guo
Jan 27, 2007·The Journal of Organic Chemistry·Xiao-Qing ZhuJin-Pei Cheng
Nov 24, 2007·The Journal of Physical Chemistry. a·Sha-Sha ChongQing-Xiang Guo
Jan 26, 2007·The Journal of Physical Chemistry. a·Xiaoguang BaoJiande Gu
Jul 13, 2007·The Journal of Physical Chemistry. a·Mansoor Namazian, Michelle L Coote
Sep 1, 2007·The Journal of Physical Chemistry. a·Ao YuJin-Pei Cheng

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