The influence of halogen-mediated interactions on halogen abstraction reactions by formyl radicals
Producción Científica
| Autores: | ; ; |
|---|---|
| Tipo de documento: | Artículo |
| Estado: | Published version |
| 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 |
| Nivel de acceso: | Acceso abierto |
| Palabra clave: | Química Física Halógenos Radicales formilo Química de radicales libres 2210 Química Física 2306 Química Orgánica |
| _version_ | 1878732333847150592 |
|---|---|
| author | Miranda, Matias O. |
| author2 | Duarte, Darío Jorge Roberto Rayón Rico, Víctor Manuel |
| author2_role | author author |
| author_browse | Duarte, Darío Jorge Roberto Miranda, Matias O. Rayón Rico, Víctor Manuel |
| author_facet | Miranda, Matias O. Duarte, Darío Jorge Roberto Rayón Rico, Víctor Manuel |
| author_role | author |
| collection | UVaDOC. Repositorio Documental de la Universidad de Valladolid |
| description | Producción Científica |
| eu_rights_str_mv | openAccess |
| format | article |
| id | ES_4101a2195c77ec61ba8f7fb59c8fdb82 |
| institution | Universidad de Valladolid |
| instname_str | Universidad de Valladolid |
| network_acronym_str | ES |
| network_name_str | España |
| oai_identifier_str | oai:uvadoc.uva.es:10324/77295 |
| publishDate | 2025 |
| publishDateSort | 2025 |
| publisher | Royal Society chemistry |
| publisherStr | Royal Society chemistry |
| reponame_str | UVaDOC. Repositorio Documental de la Universidad de Valladolid |
| spelling | The influence of halogen-mediated interactions on halogen abstraction reactions by formyl radicals Miranda, Matias O. Duarte, Darío Jorge Roberto Rayón Rico, Víctor Manuel Química Física Halógenos Radicales formilo Química de radicales libres 2210 Química Física 2306 Química Orgánica Producción Científica This 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-22V002 Ministerio de Ciencia e Innovación (MCIN) / Agencia Estatal de Investigación (AEI): PID2020- 117742GB-I00 (MCIN/AEI/10.13039/501100011033) Royal Society chemistry https://doi.org/10.1039/D4CP03882G https://uvadoc.uva.es/handle/10324/77295 |
| 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 |
| status_str | publishedVersion |
| title | 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_short | 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 |
| topic | Química Física Halógenos Radicales formilo Química de radicales libres 2210 Química Física 2306 Química Orgánica |
| topic_facet | Química Física Halógenos Radicales formilo Química de radicales libres 2210 Química Física 2306 Química Orgánica |
| url | https://doi.org/10.1039/D4CP03882G https://uvadoc.uva.es/handle/10324/77295 |