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Influence of fluorination on the conformational properties and hydrogen-bond acidity of benzyl alcohol derivatives

Influence of fluorination on the conformational properties and hydrogen-bond acidity of benzyl alcohol derivatives
Influence of fluorination on the conformational properties and hydrogen-bond acidity of benzyl alcohol derivatives
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.
hydrogen-bond acidity, benzylic alcohols, conformation analysis, fluorine
0947-6539
11462-11474
Bogdan, Elena
bd2b4c26-9ae0-42eb-8397-3c8d95f48060
Compain, Guillaume
8ce9177d-a363-49c5-a51b-af3b4184b8e8
Mtashobya, Lewis
7e000614-c31f-43fb-96da-75bf6cf2076d
Le Questel, Jean-Yves
38aea4ae-64a3-43b7-8049-ea2f351459f2
Besseau, François
436e47fa-e4a7-4a44-b5e4-476eb04184d9
Galland, Nicolas
631c189a-ea3e-4149-9f23-abec8e26e47b
Linclau, Bruno
19b9cacd-b8e8-4c65-af36-6352cade84ba
Graton, Jérôme
12432694-552e-4a40-9935-9ff7c77fbf07
Bogdan, Elena
bd2b4c26-9ae0-42eb-8397-3c8d95f48060
Compain, Guillaume
8ce9177d-a363-49c5-a51b-af3b4184b8e8
Mtashobya, Lewis
7e000614-c31f-43fb-96da-75bf6cf2076d
Le Questel, Jean-Yves
38aea4ae-64a3-43b7-8049-ea2f351459f2
Besseau, François
436e47fa-e4a7-4a44-b5e4-476eb04184d9
Galland, Nicolas
631c189a-ea3e-4149-9f23-abec8e26e47b
Linclau, Bruno
19b9cacd-b8e8-4c65-af36-6352cade84ba
Graton, Jérôme
12432694-552e-4a40-9935-9ff7c77fbf07

Bogdan, Elena, Compain, Guillaume, Mtashobya, Lewis, Le Questel, Jean-Yves, Besseau, François, Galland, Nicolas, Linclau, Bruno and Graton, Jérôme (2015) Influence of fluorination on the conformational properties and hydrogen-bond acidity of benzyl alcohol derivatives. Chemistry - A European Journal, 21 (32), 11462-11474. (doi:10.1002/chem.201501171).

Record type: Article

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.

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Published date: 30 June 2015
Keywords: hydrogen-bond acidity, benzylic alcohols, conformation analysis, fluorine
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow

Identifiers

Local EPrints ID: 381092
URI: https://eprints.soton.ac.uk/id/eprint/381092
ISSN: 0947-6539
PURE UUID: 26de37e4-f9f2-4664-96e7-3ecd468aed3d
ORCID for Bruno Linclau: ORCID iD orcid.org/0000-0001-8762-0170

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Date deposited: 22 Sep 2015 16:04
Last modified: 19 Jul 2019 01:04

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