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Energetics of Electron Pairs in Electrophilic Aromatic Substitutions

The interacting quantum atoms approach (IQA) as applied to the electron-pair exhaustive partition of real space induced by the electron localization function (ELF) is used to examine candidate energetic descriptors to rationalize substituent effects in simple electrophilic aromatic substitutions. It...

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Autores principales: Munárriz, Julen, Gallegos, Miguel, Contreras-García, Julia, Martín Pendás, Ángel
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7835785/
https://www.ncbi.nlm.nih.gov/pubmed/33478091
http://dx.doi.org/10.3390/molecules26020513
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author Munárriz, Julen
Gallegos, Miguel
Contreras-García, Julia
Martín Pendás, Ángel
author_facet Munárriz, Julen
Gallegos, Miguel
Contreras-García, Julia
Martín Pendás, Ángel
author_sort Munárriz, Julen
collection PubMed
description The interacting quantum atoms approach (IQA) as applied to the electron-pair exhaustive partition of real space induced by the electron localization function (ELF) is used to examine candidate energetic descriptors to rationalize substituent effects in simple electrophilic aromatic substitutions. It is first shown that inductive and mesomeric effects can be recognized from the decay mode of the aromatic valence bond basin populations with the distance to the substituent, and that the fluctuation of the population of adjacent bonds holds also regioselectivity information. With this, the kinetic energy of the electrons in these aromatic basins, as well as their mutual exchange-correlation energies are proposed as suitable energetic indices containing relevant information about substituent effects. We suggest that these descriptors could be used to build future reactive force fields.
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spelling pubmed-78357852021-01-27 Energetics of Electron Pairs in Electrophilic Aromatic Substitutions Munárriz, Julen Gallegos, Miguel Contreras-García, Julia Martín Pendás, Ángel Molecules Article The interacting quantum atoms approach (IQA) as applied to the electron-pair exhaustive partition of real space induced by the electron localization function (ELF) is used to examine candidate energetic descriptors to rationalize substituent effects in simple electrophilic aromatic substitutions. It is first shown that inductive and mesomeric effects can be recognized from the decay mode of the aromatic valence bond basin populations with the distance to the substituent, and that the fluctuation of the population of adjacent bonds holds also regioselectivity information. With this, the kinetic energy of the electrons in these aromatic basins, as well as their mutual exchange-correlation energies are proposed as suitable energetic indices containing relevant information about substituent effects. We suggest that these descriptors could be used to build future reactive force fields. MDPI 2021-01-19 /pmc/articles/PMC7835785/ /pubmed/33478091 http://dx.doi.org/10.3390/molecules26020513 Text en © 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Munárriz, Julen
Gallegos, Miguel
Contreras-García, Julia
Martín Pendás, Ángel
Energetics of Electron Pairs in Electrophilic Aromatic Substitutions
title Energetics of Electron Pairs in Electrophilic Aromatic Substitutions
title_full Energetics of Electron Pairs in Electrophilic Aromatic Substitutions
title_fullStr Energetics of Electron Pairs in Electrophilic Aromatic Substitutions
title_full_unstemmed Energetics of Electron Pairs in Electrophilic Aromatic Substitutions
title_short Energetics of Electron Pairs in Electrophilic Aromatic Substitutions
title_sort energetics of electron pairs in electrophilic aromatic substitutions
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7835785/
https://www.ncbi.nlm.nih.gov/pubmed/33478091
http://dx.doi.org/10.3390/molecules26020513
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AT gallegosmiguel energeticsofelectronpairsinelectrophilicaromaticsubstitutions
AT contrerasgarciajulia energeticsofelectronpairsinelectrophilicaromaticsubstitutions
AT martinpendasangel energeticsofelectronpairsinelectrophilicaromaticsubstitutions