Enthalpies of Adduct Formation between Boron Trifluoride and Selected Organic Bases in Solution: Toward an Accurate Theoretical Entry to Lewis Basicity

The Lewis basicity of selected organic bases, modeled by the enthalpies of adduct formation between gaseous BF<sub>3</sub> and bases in dichloromethane (DCM) solution, is critically examined. Although experimental enthalpies for a large number of molecules have been reported in the liter...

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Autores principales:	Jean-François Gal, Pierre-Charles Maria, Manuel Yáñez, Otilia Mó
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	BF<sub>3</sub> enthalpies Lewis basicity specific solvation high-level ab initio calculations dichloromethane boron trifluoride Organic chemistry QD241-441
Acceso en línea:	https://doaj.org/article/23f0a1627d1a4212825a5e7c5e24ee61
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spelling	oai:doaj.org-article:23f0a1627d1a4212825a5e7c5e24ee612021-11-11T18:37:51ZEnthalpies of Adduct Formation between Boron Trifluoride and Selected Organic Bases in Solution: Toward an Accurate Theoretical Entry to Lewis Basicity10.3390/molecules262166591420-3049https://doaj.org/article/23f0a1627d1a4212825a5e7c5e24ee612021-11-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/21/6659https://doaj.org/toc/1420-3049The Lewis basicity of selected organic bases, modeled by the enthalpies of adduct formation between gaseous BF<sub>3</sub> and bases in dichloromethane (DCM) solution, is critically examined. Although experimental enthalpies for a large number of molecules have been reported in the literature, it may be desirable to estimate missing or uncertain data for important Lewis bases. We decided to use high-level ab initio procedures, combined with a polarized continuum solvation model, in which the solvated species were the clusters formed by specific hydrogen bonding of DCM with the Lewis base and the Lewis base/BF<sub>3</sub> adduct. This mode of interaction with DCM corresponds to a specific solvation model (SSM). The results essentially showed that the enthalpy of BF<sub>3</sub> adduct formation in DCM solution was clearly influenced by specific interactions, with DCM acting as hydrogen-bonding donor (HBD) molecule in two ways: base/DCM and adduct/DCM, confirming that specific solvation is an important contribution to experimentally determined Lewis basicity scales. This analysis allowed us to conclude that there are reasons to suspect some gas-phase values to be in error by more than the stated experimental uncertainty. Some experimental values in DCM solution that were uncertain for identified reasons could be complemented by the computed values.Jean-François GalPierre-Charles MariaManuel YáñezOtilia MóMDPI AGarticleBF<sub>3</sub> enthalpiesLewis basicityspecific solvationhigh-level ab initio calculationsdichloromethaneboron trifluorideOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6659, p 6659 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	BF<sub>3</sub> enthalpies Lewis basicity specific solvation high-level ab initio calculations dichloromethane boron trifluoride Organic chemistry QD241-441
spellingShingle	BF<sub>3</sub> enthalpies Lewis basicity specific solvation high-level ab initio calculations dichloromethane boron trifluoride Organic chemistry QD241-441 Jean-François Gal Pierre-Charles Maria Manuel Yáñez Otilia Mó Enthalpies of Adduct Formation between Boron Trifluoride and Selected Organic Bases in Solution: Toward an Accurate Theoretical Entry to Lewis Basicity
description	The Lewis basicity of selected organic bases, modeled by the enthalpies of adduct formation between gaseous BF<sub>3</sub> and bases in dichloromethane (DCM) solution, is critically examined. Although experimental enthalpies for a large number of molecules have been reported in the literature, it may be desirable to estimate missing or uncertain data for important Lewis bases. We decided to use high-level ab initio procedures, combined with a polarized continuum solvation model, in which the solvated species were the clusters formed by specific hydrogen bonding of DCM with the Lewis base and the Lewis base/BF<sub>3</sub> adduct. This mode of interaction with DCM corresponds to a specific solvation model (SSM). The results essentially showed that the enthalpy of BF<sub>3</sub> adduct formation in DCM solution was clearly influenced by specific interactions, with DCM acting as hydrogen-bonding donor (HBD) molecule in two ways: base/DCM and adduct/DCM, confirming that specific solvation is an important contribution to experimentally determined Lewis basicity scales. This analysis allowed us to conclude that there are reasons to suspect some gas-phase values to be in error by more than the stated experimental uncertainty. Some experimental values in DCM solution that were uncertain for identified reasons could be complemented by the computed values.
format	article
author	Jean-François Gal Pierre-Charles Maria Manuel Yáñez Otilia Mó
author_facet	Jean-François Gal Pierre-Charles Maria Manuel Yáñez Otilia Mó
author_sort	Jean-François Gal
title	Enthalpies of Adduct Formation between Boron Trifluoride and Selected Organic Bases in Solution: Toward an Accurate Theoretical Entry to Lewis Basicity
title_short	Enthalpies of Adduct Formation between Boron Trifluoride and Selected Organic Bases in Solution: Toward an Accurate Theoretical Entry to Lewis Basicity
title_full	Enthalpies of Adduct Formation between Boron Trifluoride and Selected Organic Bases in Solution: Toward an Accurate Theoretical Entry to Lewis Basicity
title_fullStr	Enthalpies of Adduct Formation between Boron Trifluoride and Selected Organic Bases in Solution: Toward an Accurate Theoretical Entry to Lewis Basicity
title_full_unstemmed	Enthalpies of Adduct Formation between Boron Trifluoride and Selected Organic Bases in Solution: Toward an Accurate Theoretical Entry to Lewis Basicity
title_sort	enthalpies of adduct formation between boron trifluoride and selected organic bases in solution: toward an accurate theoretical entry to lewis basicity
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/23f0a1627d1a4212825a5e7c5e24ee61
work_keys_str_mv	AT jeanfrancoisgal enthalpiesofadductformationbetweenborontrifluorideandselectedorganicbasesinsolutiontowardanaccuratetheoreticalentrytolewisbasicity AT pierrecharlesmaria enthalpiesofadductformationbetweenborontrifluorideandselectedorganicbasesinsolutiontowardanaccuratetheoreticalentrytolewisbasicity AT manuelyanez enthalpiesofadductformationbetweenborontrifluorideandselectedorganicbasesinsolutiontowardanaccuratetheoreticalentrytolewisbasicity AT otiliamo enthalpiesofadductformationbetweenborontrifluorideandselectedorganicbasesinsolutiontowardanaccuratetheoreticalentrytolewisbasicity
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Enthalpies of Adduct Formation between Boron Trifluoride and Selected Organic Bases in Solution: Toward an Accurate Theoretical Entry to Lewis Basicity

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