| dc.creator |
Bogdan, Elena |
|
| dc.creator |
Compain, Guillaume |
|
| dc.creator |
Mtashobya, Lewis |
|
| dc.creator |
Le Questel, Jean-Yves |
|
| dc.creator |
Besseau, François |
|
| dc.creator |
Galland, Nicolas |
|
| dc.creator |
Linclau, Bruno |
|
| dc.creator |
Graton, Jérôme |
|
| dc.date |
2017-03-09T08:37:50Z |
|
| dc.date |
2017-03-09T08:37:50Z |
|
| dc.date |
2015 |
|
| dc.date.accessioned |
2018-04-18T12:08:00Z |
|
| dc.date.available |
2018-04-18T12:08:00Z |
|
| dc.identifier |
http://onlinelibrary.wiley.com/doi/10.1002/chem.201501171/pdf |
|
| dc.identifier |
http://hdl.handle.net/20.500.11810/4491 |
|
| dc.identifier.uri |
http://hdl.handle.net/20.500.11810/4491 |
|
| dc.description |
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. |
|
| dc.description |
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 |
|
| dc.language |
en |
|
| dc.publisher |
WILEY-VCH Verlag |
|
| dc.subject |
hydrogen-bond acidity · benzylic alcohols · conformation analysis · fluorine |
|
| dc.title |
Influence of Fluorination on the Conformational Properties and Hydrogen-Bond Acidity of Benzyl Alcohol Derivatives |
|
| dc.type |
Journal Article, Peer Reviewed |
|