Influence of Fluorination on the Conformational Properties and Hydrogen-Bond Acidity of Benzyl Alcohol Derivatives

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dc.creatorBogdan, Elena
dc.creatorCompain, Guillaume
dc.creatorMtashobya, Lewis
dc.creatorLe Questel, Jean-Yves
dc.creatorBesseau, François
dc.creatorGalland, Nicolas
dc.creatorLinclau, Bruno
dc.creatorGraton, Jérôme
dc.date2017-03-09T08:37:50Z
dc.date2017-03-09T08:37:50Z
dc.date2015
dc.date.accessioned2018-04-18T12:08:00Z
dc.date.available2018-04-18T12:08:00Z
dc.descriptionAbstract: 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.
dc.descriptiongrant (ANR-13-JS08–0007-01), grant EP/K016938/1, allocation c2014085117, (grant ANR-11-EQPX-0004 funded by the ANR, CCIPL for grants of computer time, EP/K039466/1 and L.M. thanks Mkwawa University College of Education for financial support
dc.identifierhttp://onlinelibrary.wiley.com/doi/10.1002/chem.201501171/pdf
dc.identifierhttp://hdl.handle.net/20.500.11810/4491
dc.identifier.urihttp://hdl.handle.net/20.500.11810/4491
dc.languageen
dc.publisherWILEY-VCH Verlag
dc.subjecthydrogen-bond acidity · benzylic alcohols · conformation analysis · fluorine
dc.titleInfluence of Fluorination on the Conformational Properties and Hydrogen-Bond Acidity of Benzyl Alcohol Derivatives
dc.typeJournal Article, Peer Reviewed

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