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Ab initio studies of the effect of the fluorination on deprotonation reaction of the benzene sulfonic acid

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Abstract

We carried out quantum chemical calculations to analyze the effects of fluorination on the activation energy (Ea) of sulfonic group deprotonation by water molecules. The model molecule was 2,3,4,5,6-pentafluorobenzenesulfonic acid (5FBSA), which was obtained by substituting all aromatic hydrogen atoms of benzenesulfonic acid (BSA) for fluorine atoms. The target hydration level was three. Our analysis indicated that the Ea of deprotonation in 5FBSA was lower than that of BSA, suggesting that the cation of 5FBSA was stabilized. Previous studies have reported that fluorinated molecules have a lower Ea to deprotonation and a stabilized deprotonated state even at a hydration level of three. This effect is attributed to the strong electron withdrawing ability of fluorine. However, compared with non-aromatic molecules, the Ea of deprotonation of aromatic molecules is slightly higher, and the overall energy change (ΔE) is lower, even if the molecule is fluorinated.

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Acknowledgments

This research is financially supported by the New Energy and Industrial Technology Development Organization (NEDO). All calculations were carried out by the computer of the Advanced Fluid Information Research Center, Tohoku University.

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Authors and Affiliations

  1. Faculty of Engineering, University of Fukui, 3-9-1, Bunkyo, Fukui, Fukui, 910-8507, Japan

    Akinori Fukushima

  2. Institute of Fluid Science, Tohoku University, 2-1-1, Katahira, Sendai, Miyagi, 980-8577, Japan

    Hironori Sakai & Takashi Tokumasu

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  1. Akinori Fukushima
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  2. Hironori Sakai
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  3. Takashi Tokumasu
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Correspondence to Akinori Fukushima.

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Fukushima, A., Sakai, H. & Tokumasu, T. Ab initio studies of the effect of the fluorination on deprotonation reaction of the benzene sulfonic acid. J Mol Model 26, 127 (2020). https://doi.org/10.1007/s00894-020-04402-8

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