Relativistic effects on NMR parameters of halogen-bonded complexes

Relativistic effects are found to be important for the estimation of NMR parameters in halogen-bonded complexes, mainly when they involve the heavier elements, iodine and astatine. A detailed study of 60 binary complexes formed between dihalogen molecules (XY with X, Y = F, Cl, Br, I and At) and fou...

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Detalles Bibliográficos
Autores: Alkorta, Ibon, Elguero, José, Yáñez Montero, Manuel, Mo Romero, Otilia, Montero Campillo, M. Merced
Tipo de recurso: artículo
Fecha de publicación:2019
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/718882
Acceso en línea:http://hdl.handle.net/10486/718882
https://dx.doi.org/10.3390/molecules24234399
Access Level:acceso abierto
Palabra clave:Halogen bonding
astatine
relativistic effects
NMR
absolute shieldings
nuclear quadrupolar coupling constants
Química
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repository_id_str
spelling Relativistic effects on NMR parameters of halogen-bonded complexesAlkorta, IbonElguero, JoséYáñez Montero, ManuelMo Romero, OtiliaMontero Campillo, M. MercedHalogen bondingastatinerelativistic effectsNMRabsolute shieldingsnuclear quadrupolar coupling constantsQuímicaRelativistic effects are found to be important for the estimation of NMR parameters in halogen-bonded complexes, mainly when they involve the heavier elements, iodine and astatine. A detailed study of 60 binary complexes formed between dihalogen molecules (XY with X, Y = F, Cl, Br, I and At) and four Lewis bases (NH3, H2O, PH3 and SH2) was carried out at the MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP computational level to show the extent of these e ects. The NMR parameters (shielding and nuclear quadrupolar coupling constants) were computed using the relativistic Hamiltonian ZORA and compared to the values obtained with a non-relativistic Hamiltonian. The results show a mixture of the importance of the relativistic corrections as both the size of the halogen atom and the proximity of this atom to the basic site of the Lewis base increaseFinancial support from the Ministerio de Ciencia, Innovación y Universidades (projects PGC2018-094644-B-C21, PGC2018-094644-B-C22 and CTQ2016-76061-P) and Comunidad de Madrid (P2018/EMT-4329 AIRTEC-CM). The authors want to thank the CTI (CSIC) for the computational resourcesMDPI AGDepartamento de QuímicaFacultad de Ciencias20192019-12-02research articlehttp://purl.org/coar/resource_type/c_2df8fbb1VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/718882https://dx.doi.org/10.3390/molecules24234399reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/7188822026-06-23T12:46:27Z
dc.title.none.fl_str_mv Relativistic effects on NMR parameters of halogen-bonded complexes
title Relativistic effects on NMR parameters of halogen-bonded complexes
spellingShingle Relativistic effects on NMR parameters of halogen-bonded complexes
Alkorta, Ibon
Halogen bonding
astatine
relativistic effects
NMR
absolute shieldings
nuclear quadrupolar coupling constants
Química
title_short Relativistic effects on NMR parameters of halogen-bonded complexes
title_full Relativistic effects on NMR parameters of halogen-bonded complexes
title_fullStr Relativistic effects on NMR parameters of halogen-bonded complexes
title_full_unstemmed Relativistic effects on NMR parameters of halogen-bonded complexes
title_sort Relativistic effects on NMR parameters of halogen-bonded complexes
dc.creator.none.fl_str_mv Alkorta, Ibon
Elguero, José
Yáñez Montero, Manuel
Mo Romero, Otilia
Montero Campillo, M. Merced
author Alkorta, Ibon
author_facet Alkorta, Ibon
Elguero, José
Yáñez Montero, Manuel
Mo Romero, Otilia
Montero Campillo, M. Merced
author_role author
author2 Elguero, José
Yáñez Montero, Manuel
Mo Romero, Otilia
Montero Campillo, M. Merced
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Departamento de Química
Facultad de Ciencias
dc.subject.none.fl_str_mv Halogen bonding
astatine
relativistic effects
NMR
absolute shieldings
nuclear quadrupolar coupling constants
Química
topic Halogen bonding
astatine
relativistic effects
NMR
absolute shieldings
nuclear quadrupolar coupling constants
Química
description Relativistic effects are found to be important for the estimation of NMR parameters in halogen-bonded complexes, mainly when they involve the heavier elements, iodine and astatine. A detailed study of 60 binary complexes formed between dihalogen molecules (XY with X, Y = F, Cl, Br, I and At) and four Lewis bases (NH3, H2O, PH3 and SH2) was carried out at the MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP computational level to show the extent of these e ects. The NMR parameters (shielding and nuclear quadrupolar coupling constants) were computed using the relativistic Hamiltonian ZORA and compared to the values obtained with a non-relativistic Hamiltonian. The results show a mixture of the importance of the relativistic corrections as both the size of the halogen atom and the proximity of this atom to the basic site of the Lewis base increase
publishDate 2019
dc.date.none.fl_str_mv 2019
2019-12-02
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/10486/718882
https://dx.doi.org/10.3390/molecules24234399
url http://hdl.handle.net/10486/718882
https://dx.doi.org/10.3390/molecules24234399
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 4.0 International
http://creativecommons.org/licenses/by/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 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv MDPI AG
publisher.none.fl_str_mv MDPI AG
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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