Influence of Fluorination on the Conformational Properties and Hydrogen-Bond Acidity of Benzyl Alcohol Derivatives
| dc.contributor.author | Bogdan, Elena | |
| dc.contributor.author | Compain, Guillaume | |
| dc.contributor.author | Mtashobya, Lewis | |
| dc.contributor.author | Le Questel, Jean-Yves | |
| dc.contributor.author | Besseau, François | |
| dc.contributor.author | Galland, Nicolas | |
| dc.contributor.author | Linclau, Bruno | |
| dc.contributor.author | Graton, Jérôme | |
| dc.date.accessioned | 2017-03-09T08:37:50Z | |
| dc.date.available | 2017-03-09T08:37:50Z | |
| dc.date.issued | 2015 | |
| dc.description.abstract | 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. | en_US |
| dc.description.sponsorship | grant (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 | en_US |
| dc.identifier.citation | http://onlinelibrary.wiley.com/doi/10.1002/chem.201501171/pdf | en_US |
| dc.identifier.uri | http://hdl.handle.net/20.500.11810/4491 | |
| dc.language.iso | en | en_US |
| dc.publisher | WILEY-VCH Verlag | en_US |
| dc.subject | hydrogen-bond acidity · benzylic alcohols · conformation analysis · fluorine | en_US |
| dc.title | Influence of Fluorination on the Conformational Properties and Hydrogen-Bond Acidity of Benzyl Alcohol Derivatives | en_US |
| dc.type | Journal Article, Peer Reviewed | en_US |