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Molecules 2018, 23(2), 423; https://doi.org/10.3390/molecules23020423

Microhydration and the Enhanced Acidity of Free Radicals

EaStCHEM School of Chemistry, University of St. Andrews, St. Andrews KY16 9ST, UK
Received: 31 January 2018 / Revised: 9 February 2018 / Accepted: 14 February 2018 / Published: 14 February 2018
(This article belongs to the Special Issue Radical Chemistry)
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Abstract

Recent theoretical research employing a continuum solvent model predicted that radical centers would enhance the acidity (RED-shift) of certain proton-donor molecules. Microhydration studies employing a DFT method are reported here with the aim of establishing the effect of the solvent micro-structure on the acidity of radicals with and without RED-shifts. Microhydration cluster structures were obtained for carboxyl, carboxy-ethynyl, carboxy-methyl, and hydroperoxyl radicals. The numbers of water molecules needed to induce spontaneous ionization were determined. The hydration clusters formed primarily round the CO2 units of the carboxylate-containing radicals. Only 4 or 5 water molecules were needed to induce ionization of carboxyl and carboxy-ethynyl radicals, thus corroborating their large RED-shifts. View Full-Text
Keywords: free radicals; acidity; DFT computations; hydration free radicals; acidity; DFT computations; hydration
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).
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Walton, J.C. Microhydration and the Enhanced Acidity of Free Radicals. Molecules 2018, 23, 423.

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