Microhydration and the enhanced acidity of free radicals
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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.
Walton , J C 2018 , ' Microhydration and the enhanced acidity of free radicals ' Molecules , vol. 23 , no. 2 , 423 . DOI: 10.3390/molecules23020423
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DescriptionThe author thanks EaStCHEM for financial support.
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