Hydride and halide abstraction reactions behind the enhanced basicity of Be and Mg clusters with nitrogen bases

In this study, we investigate the protonation effects on the structure, relative stability and basicity of complexes formed by the interaction of monomers and dimers of BeX2 and MgX2 (X = H, F) with NH3, CH2NH, HCN, and NC5H5 bases. Calculations were performed using the M06-2X/aug-cc-pVTZ formalism,...

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Autores: Yáñez Montero, Manuel, Mo Romero, Otilia, Montero Campillo, M. Merced, Alkorta Osoro, Ibon, Elguero, José
Tipo de documento: artigo
Data de publicação:2025
País:España
Recursos:Universidad Autónoma de Madrid
Repositório:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglês
OAI Identifier:oai:repositorio.uam.es:10486/718210
Acesso em linha:http://hdl.handle.net/10486/718210
https://dx.doi.org/10.1002/jcc.27509
Access Level:Acceso aberto
Palavra-chave:DFT calculations
fluoride abstraction
hydride abstraction
intrinsic basicity
Mg and Be clusters
nitrogen bases
Química
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spelling Hydride and halide abstraction reactions behind the enhanced basicity of Be and Mg clusters with nitrogen basesYáñez Montero, ManuelMo Romero, OtiliaMontero Campillo, M. MercedAlkorta Osoro, IbonElguero, JoséDFT calculationsfluoride abstractionhydride abstractionintrinsic basicityMg and Be clustersnitrogen basesQuímicaIn this study, we investigate the protonation effects on the structure, relative stability and basicity of complexes formed by the interaction of monomers and dimers of BeX2 and MgX2 (X = H, F) with NH3, CH2NH, HCN, and NC5H5 bases. Calculations were performed using the M06-2X/aug-cc-pVTZ formalism, along with QTAIM, ELF and NCI methods for electron density analysis and MBIE and LMO-EDA energy decomposition analyses for interaction enthalpies. The protonation of the MH2– and M2H4–Base complexes occurs at the negatively charged hydrogen atoms of the MH2 and M2H4 moieties through typical hydride abstraction reactions, while protonation at the N atom of the base is systematically less exothermic. The preference for the hydride transfer mechanism is directly associated with the significant exothermicity of H2 formation through the interaction between H− and H+, and the high hydride donor ability of these complexes. The basicity of both, MH2 and M2H4 compounds increases enormously upon association with the corresponding bases, with the increase exceeding 40 orders of magnitude in terms of ionization constants. Due to the smaller exothermicity of HF formation, the basicity of fluorides is lower than that of hydrides. In Be complexes, the protonation at the N atom of the base dominates over the fluoride abstraction mechanism. However, for the Mg complexes the fluoride abstraction mechanism is energetically the most favorable process, reflecting the greater facility of Mg complexes to lose F−This work was carried out with financial support from the projects PID2021-125207NB-C31 and PID2021-125207NB-C32 of the Ministerio de Ciencia, Innovación y Universidades of Spain (MICINN) and the project Y2020/EMT-6290 (PRIES-CM) of the Comunidad de Madrid. Finally, the authors thank the Centro de Computación Científica of the UAM (CCC-UAM) for the generous allocation of computer time and continued technical supportDepartamento de QuímicaFacultad de Ciencias20252025-01-05research articlehttp://purl.org/coar/resource_type/c_2df8fbb1VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/718210https://dx.doi.org/10.1002/jcc.27509reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/7182102026-06-23T12:46:27Z
dc.title.none.fl_str_mv Hydride and halide abstraction reactions behind the enhanced basicity of Be and Mg clusters with nitrogen bases
title Hydride and halide abstraction reactions behind the enhanced basicity of Be and Mg clusters with nitrogen bases
spellingShingle Hydride and halide abstraction reactions behind the enhanced basicity of Be and Mg clusters with nitrogen bases
Yáñez Montero, Manuel
DFT calculations
fluoride abstraction
hydride abstraction
intrinsic basicity
Mg and Be clusters
nitrogen bases
Química
title_short Hydride and halide abstraction reactions behind the enhanced basicity of Be and Mg clusters with nitrogen bases
title_full Hydride and halide abstraction reactions behind the enhanced basicity of Be and Mg clusters with nitrogen bases
title_fullStr Hydride and halide abstraction reactions behind the enhanced basicity of Be and Mg clusters with nitrogen bases
title_full_unstemmed Hydride and halide abstraction reactions behind the enhanced basicity of Be and Mg clusters with nitrogen bases
title_sort Hydride and halide abstraction reactions behind the enhanced basicity of Be and Mg clusters with nitrogen bases
dc.creator.none.fl_str_mv Yáñez Montero, Manuel
Mo Romero, Otilia
Montero Campillo, M. Merced
Alkorta Osoro, Ibon
Elguero, José
author Yáñez Montero, Manuel
author_facet Yáñez Montero, Manuel
Mo Romero, Otilia
Montero Campillo, M. Merced
Alkorta Osoro, Ibon
Elguero, José
author_role author
author2 Mo Romero, Otilia
Montero Campillo, M. Merced
Alkorta Osoro, Ibon
Elguero, José
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Departamento de Química
Facultad de Ciencias
dc.subject.none.fl_str_mv DFT calculations
fluoride abstraction
hydride abstraction
intrinsic basicity
Mg and Be clusters
nitrogen bases
Química
topic DFT calculations
fluoride abstraction
hydride abstraction
intrinsic basicity
Mg and Be clusters
nitrogen bases
Química
description In this study, we investigate the protonation effects on the structure, relative stability and basicity of complexes formed by the interaction of monomers and dimers of BeX2 and MgX2 (X = H, F) with NH3, CH2NH, HCN, and NC5H5 bases. Calculations were performed using the M06-2X/aug-cc-pVTZ formalism, along with QTAIM, ELF and NCI methods for electron density analysis and MBIE and LMO-EDA energy decomposition analyses for interaction enthalpies. The protonation of the MH2– and M2H4–Base complexes occurs at the negatively charged hydrogen atoms of the MH2 and M2H4 moieties through typical hydride abstraction reactions, while protonation at the N atom of the base is systematically less exothermic. The preference for the hydride transfer mechanism is directly associated with the significant exothermicity of H2 formation through the interaction between H− and H+, and the high hydride donor ability of these complexes. The basicity of both, MH2 and M2H4 compounds increases enormously upon association with the corresponding bases, with the increase exceeding 40 orders of magnitude in terms of ionization constants. Due to the smaller exothermicity of HF formation, the basicity of fluorides is lower than that of hydrides. In Be complexes, the protonation at the N atom of the base dominates over the fluoride abstraction mechanism. However, for the Mg complexes the fluoride abstraction mechanism is energetically the most favorable process, reflecting the greater facility of Mg complexes to lose F−
publishDate 2025
dc.date.none.fl_str_mv 2025
2025-01-05
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10486/718210
https://dx.doi.org/10.1002/jcc.27509
url http://hdl.handle.net/10486/718210
https://dx.doi.org/10.1002/jcc.27509
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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