The influence of halogen-mediated interactions on halogen abstraction reactions by formyl radicals

Producción Científica

Detalles Bibliográficos
Autores: Miranda, Matias O., Duarte, Darío Jorge Roberto, Rayón Rico, Víctor Manuel
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Universidad de Valladolid
Repositorio:UVaDOC. Repositorio Documental de la Universidad de Valladolid
OAI Identifier:oai:uvadoc.uva.es:10324/77295
Acceso en línea:https://doi.org/10.1039/D4CP03882G
https://uvadoc.uva.es/handle/10324/77295
Access Level:acceso abierto
Palabra clave:Química Física
Halógenos
Radicales formilo
Química de radicales libres
2210 Química Física
2306 Química Orgánica
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oai_identifier_str oai:uvadoc.uva.es:10324/77295
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spelling The influence of halogen-mediated interactions on halogen abstraction reactions by formyl radicalsMiranda, Matias O.Duarte, Darío Jorge RobertoRayón Rico, Víctor ManuelQuímica FísicaHalógenosRadicales formiloQuímica de radicales libres2210 Química Física2306 Química OrgánicaProducción CientíficaThis article reports a theoretical study on the halogen exchange reactions YX + CHO → Y + XCHO (with Y = F, Cl, Br; X = Cl, Br, I) carried out at a high level of accuracy using coupled-cluster based methodologies including CCSD(T)-F12, CCSD(T)/CBS and CCSDT(Q)Λ. Most of the reactions are exothermic at room temperature, with the exception of the reactions FI + CHO → F + ICHO and ClI + CHO → Cl + ICHO. Exothermicity follows two concurrent trends established by the strength of the bonds being cleaved and formed: Y = F < Cl < Br (X–Y bond strength) and X = Cl > Br > I (C–X bond strength). Regarding the topology of the potential energy surfaces, we find that at the CCSD level of theory only some processes present the expected reaction profile: a pre-reactive complex (preRC) followed by a transition state (TS) and a post-reactive complex (postRC). However, when triple excitations are taken into account, all reactions become barrierless with no preRC/TS along the reaction profile. We propose that halogen-mediated interactions through the σ-hole, which represent the driving force in the early stages of the title reactions, are responsible for the absence of a tight transition state. We suggest that the strength of these interactions formed during these processes triggers the onset of the halogen atom exchange, before the preRC is formed. Therefore, this study aims to show the relevant role of halogen-mediated interactions in the mechanism of reactions in which a halogen atom is abstracted by the formyl radical (CHO).Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET) / Asociación Universitaria Iberoamericana de Postgrado (AUIP)Secretaría General de Ciencia y Tecnoclogía (SGCT) - UNNE: PI-22V002Ministerio de Ciencia e Innovación (MCIN) / Agencia Estatal de Investigación (AEI): PID2020- 117742GB-I00 (MCIN/AEI/10.13039/501100011033)Royal Society chemistry2025info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://doi.org/10.1039/D4CP03882Ghttps://uvadoc.uva.es/handle/10324/77295reponame:UVaDOC. Repositorio Documental de la Universidad de Valladolidinstname:Universidad de ValladolidIngléshttps://pubs.rsc.org/en/content/articlelanding/2025/cp/d4cp03882ginfo:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by/3.0/oai:uvadoc.uva.es:10324/772952026-06-13T12:44:47Z
dc.title.none.fl_str_mv The influence of halogen-mediated interactions on halogen abstraction reactions by formyl radicals
title The influence of halogen-mediated interactions on halogen abstraction reactions by formyl radicals
spellingShingle The influence of halogen-mediated interactions on halogen abstraction reactions by formyl radicals
Miranda, Matias O.
Química Física
Halógenos
Radicales formilo
Química de radicales libres
2210 Química Física
2306 Química Orgánica
title_short The influence of halogen-mediated interactions on halogen abstraction reactions by formyl radicals
title_full The influence of halogen-mediated interactions on halogen abstraction reactions by formyl radicals
title_fullStr The influence of halogen-mediated interactions on halogen abstraction reactions by formyl radicals
title_full_unstemmed The influence of halogen-mediated interactions on halogen abstraction reactions by formyl radicals
title_sort The influence of halogen-mediated interactions on halogen abstraction reactions by formyl radicals
dc.creator.none.fl_str_mv Miranda, Matias O.
Duarte, Darío Jorge Roberto
Rayón Rico, Víctor Manuel
author Miranda, Matias O.
author_facet Miranda, Matias O.
Duarte, Darío Jorge Roberto
Rayón Rico, Víctor Manuel
author_role author
author2 Duarte, Darío Jorge Roberto
Rayón Rico, Víctor Manuel
author2_role author
author
dc.subject.none.fl_str_mv Química Física
Halógenos
Radicales formilo
Química de radicales libres
2210 Química Física
2306 Química Orgánica
topic Química Física
Halógenos
Radicales formilo
Química de radicales libres
2210 Química Física
2306 Química Orgánica
description Producción Científica
publishDate 2025
dc.date.none.fl_str_mv 2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://doi.org/10.1039/D4CP03882G
https://uvadoc.uva.es/handle/10324/77295
url https://doi.org/10.1039/D4CP03882G
https://uvadoc.uva.es/handle/10324/77295
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv https://pubs.rsc.org/en/content/articlelanding/2025/cp/d4cp03882g
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by/3.0/
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by/3.0/
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society chemistry
publisher.none.fl_str_mv Royal Society chemistry
dc.source.none.fl_str_mv reponame:UVaDOC. Repositorio Documental de la Universidad de Valladolid
instname:Universidad de Valladolid
instname_str Universidad de Valladolid
reponame_str UVaDOC. Repositorio Documental de la Universidad de Valladolid
collection UVaDOC. Repositorio Documental de la Universidad de Valladolid
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.81155

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