Browsing by Author "Bogdan, Elena"

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    Influence of Alcohol β‐Fluorination on Hydrogen‐Bond Acidity of Conformationally Flexible Substrates
    (Wiley Online Library, 2016) Graton, Jérôme; Compain, Guillaume; Besseau, François; Bogdan, Elena; Watts, Joe; Mtashobya, Lewis; Wang, Zhong; Weymouth-Wilson, Alex; Galland, Nicolas; Questel, Jean-Yves Le; Linclau, Bruno
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    Influence of Fluorination on the Conformational Properties and Hydrogen-Bond Acidity of Benzyl Alcohol Derivatives
    (WILEY-VCH Verlag, 2015) Bogdan, Elena; Compain, Guillaume; Mtashobya, Lewis; Le Questel, Jean-Yves; Besseau, François; Galland, Nicolas; Linclau, Bruno; Graton, Jérôme
    Abstract: The effect of fluorination on the conformational and hydrogen-bond (HB)-donating properties of a series of benzyl alcohols has been investigated experimentally by IR spectroscopy and theoretically with quantum chemical methods (ab initio (MP2) and DFT (MPWB1K)). It was found that o-fluorination generally resulted in an increase in the HB acidity of the hydroxyl group, whereas a decrease was observed upon o,o’-difluorination. Computational analysis showed that the conformational landscapes of the title compounds are strongly influenced by the presence of o-fluorine atoms. Intramolecular interaction descriptors based on AIM, NCI and NBO analyses reveal that, in addition to an intramolecular OH···F interaction, secondary CH···F and/or CH···O interactions also occur, contributing to the stabilisation of the various conformations, and influencing the overall HB properties of the alcohol group. The benzyl alcohol HB-donating capacity trends are properly described by an electrostatic potential based descriptor calculated at the MPWB1K/6-31+ G(d,p) level of theory, provided solvation effects are taken into account for these flexible HB donors.