NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and Mercury

Autores
Zapata Escobar, Andy Danian; Maldonado, Alejandro Fabián; Mendoza Cortes, Jose L.; Aucar, Gustavo Adolfo
Año de publicación
2023
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this article, we delve into the intricate behavior of electronic mechanisms underlying NMR magnetic shieldings (Formula presented.) in molecules containing heavy atoms, such as cadmium, platinum, and mercury. Specifically, we explore Pt (Formula presented.) (X = F, Cl, Br, I; n = 4, 6) and XCl (Formula presented.) Te (Formula presented.) (Formula presented.) H (Formula presented.) (X = Cd, Hg; Y = N, P) molecular systems. It is known that the leading electronic mechanisms responsible for the relativistic effects on (Formula presented.) are well characterized by the linear response with elimination of small components model (LRESC). In this study, we present the results obtained from the innovative LRESC-Loc model, which offers the same outcomes as the LRESC model but employs localized molecular orbitals (LMOs) instead of canonical MOs. These LMOs provide a chemist’s representation of atomic core, lone pairs, and bonds. The whole set of electronic mechanisms responsible of the relativistic effects can be expressed in terms of both non-ligand-dependent and ligand-dependent contributions. We elucidate the electronic origins of trends and behaviors exhibited by these diverse mechanisms in the aforementioned molecular systems. In Pt (Formula presented.) molecules, the predominant relativistic mechanism is the well-established one-body spin–orbit ((Formula presented.)) mechanism, while the paramagnetic mass–velocity ((Formula presented.)) and Darwin ((Formula presented.)) contributing mechanisms also demand consideration. However, in Pt (Formula presented.) molecules, the (Formula presented.) contribution surpasses that of the (Formula presented.) mechanism, thus influencing the overall ligand-dependent contributions. As for complexes containing Cd and Hg, the ligand-dependent contributions exhibit similar magnitudes when nitrogen is substituted with phosphorus. The only discrepancy arises from the (Formula presented.) contribution, which changes sign between the two molecules due to the contribution of bond orbitals between the metal and tellurium atoms.
Fil: Zapata Escobar, Andy Danian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
Fil: Maldonado, Alejandro Fabián. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
Fil: Mendoza Cortes, Jose L.. Michigan State University; Estados Unidos
Fil: Aucar, Gustavo Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
Materia
LRESC-LOC
MAGNETIC SHIELDING
RELATIVISTIC EFFECTS
TRANSITION METALS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/235959
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/235959
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and MercuryZapata Escobar, Andy DanianMaldonado, Alejandro FabiánMendoza Cortes, Jose L.Aucar, Gustavo AdolfoLRESC-LOCMAGNETIC SHIELDINGRELATIVISTIC EFFECTSTRANSITION METALShttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1In this article, we delve into the intricate behavior of electronic mechanisms underlying NMR magnetic shieldings (Formula presented.) in molecules containing heavy atoms, such as cadmium, platinum, and mercury. Specifically, we explore Pt (Formula presented.) (X = F, Cl, Br, I; n = 4, 6) and XCl (Formula presented.) Te (Formula presented.) (Formula presented.) H (Formula presented.) (X = Cd, Hg; Y = N, P) molecular systems. It is known that the leading electronic mechanisms responsible for the relativistic effects on (Formula presented.) are well characterized by the linear response with elimination of small components model (LRESC). In this study, we present the results obtained from the innovative LRESC-Loc model, which offers the same outcomes as the LRESC model but employs localized molecular orbitals (LMOs) instead of canonical MOs. These LMOs provide a chemist’s representation of atomic core, lone pairs, and bonds. The whole set of electronic mechanisms responsible of the relativistic effects can be expressed in terms of both non-ligand-dependent and ligand-dependent contributions. We elucidate the electronic origins of trends and behaviors exhibited by these diverse mechanisms in the aforementioned molecular systems. In Pt (Formula presented.) molecules, the predominant relativistic mechanism is the well-established one-body spin–orbit ((Formula presented.)) mechanism, while the paramagnetic mass–velocity ((Formula presented.)) and Darwin ((Formula presented.)) contributing mechanisms also demand consideration. However, in Pt (Formula presented.) molecules, the (Formula presented.) contribution surpasses that of the (Formula presented.) mechanism, thus influencing the overall ligand-dependent contributions. As for complexes containing Cd and Hg, the ligand-dependent contributions exhibit similar magnitudes when nitrogen is substituted with phosphorus. The only discrepancy arises from the (Formula presented.) contribution, which changes sign between the two molecules due to the contribution of bond orbitals between the metal and tellurium atoms.Fil: Zapata Escobar, Andy Danian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; ArgentinaFil: Maldonado, Alejandro Fabián. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; ArgentinaFil: Mendoza Cortes, Jose L.. Michigan State University; Estados UnidosFil: Aucar, Gustavo Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; ArgentinaMultidisciplinary Digital Publishing Institute2023-06-27info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/235959Zapata Escobar, Andy Danian; Maldonado, Alejandro Fabián; Mendoza Cortes, Jose L.; Aucar, Gustavo Adolfo; NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and Mercury; Multidisciplinary Digital Publishing Institute; Magnetochemistry; 9; 7; 27-6-2023; 1-152312-7481CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/2312-7481/9/7/165info:eu-repo/semantics/altIdentifier/doi/10.3390/magnetochemistry9070165info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:45:43Zoai:ri.conicet.gov.ar:11336/235959instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-15 14:45:43.984CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and Mercury
title NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and Mercury
spellingShingle NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and Mercury
Zapata Escobar, Andy Danian
LRESC-LOC
MAGNETIC SHIELDING
RELATIVISTIC EFFECTS
TRANSITION METALS
title_short NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and Mercury
title_full NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and Mercury
title_fullStr NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and Mercury
title_full_unstemmed NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and Mercury
title_sort NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and Mercury
dc.creator.none.fl_str_mv Zapata Escobar, Andy Danian
Maldonado, Alejandro Fabián
Mendoza Cortes, Jose L.
Aucar, Gustavo Adolfo
author Zapata Escobar, Andy Danian
author_facet Zapata Escobar, Andy Danian
Maldonado, Alejandro Fabián
Mendoza Cortes, Jose L.
Aucar, Gustavo Adolfo
author_role author
author2 Maldonado, Alejandro Fabián
Mendoza Cortes, Jose L.
Aucar, Gustavo Adolfo
author2_role author
author
author
dc.subject.none.fl_str_mv LRESC-LOC
MAGNETIC SHIELDING
RELATIVISTIC EFFECTS
TRANSITION METALS
topic LRESC-LOC
MAGNETIC SHIELDING
RELATIVISTIC EFFECTS
TRANSITION METALS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In this article, we delve into the intricate behavior of electronic mechanisms underlying NMR magnetic shieldings (Formula presented.) in molecules containing heavy atoms, such as cadmium, platinum, and mercury. Specifically, we explore Pt (Formula presented.) (X = F, Cl, Br, I; n = 4, 6) and XCl (Formula presented.) Te (Formula presented.) (Formula presented.) H (Formula presented.) (X = Cd, Hg; Y = N, P) molecular systems. It is known that the leading electronic mechanisms responsible for the relativistic effects on (Formula presented.) are well characterized by the linear response with elimination of small components model (LRESC). In this study, we present the results obtained from the innovative LRESC-Loc model, which offers the same outcomes as the LRESC model but employs localized molecular orbitals (LMOs) instead of canonical MOs. These LMOs provide a chemist’s representation of atomic core, lone pairs, and bonds. The whole set of electronic mechanisms responsible of the relativistic effects can be expressed in terms of both non-ligand-dependent and ligand-dependent contributions. We elucidate the electronic origins of trends and behaviors exhibited by these diverse mechanisms in the aforementioned molecular systems. In Pt (Formula presented.) molecules, the predominant relativistic mechanism is the well-established one-body spin–orbit ((Formula presented.)) mechanism, while the paramagnetic mass–velocity ((Formula presented.)) and Darwin ((Formula presented.)) contributing mechanisms also demand consideration. However, in Pt (Formula presented.) molecules, the (Formula presented.) contribution surpasses that of the (Formula presented.) mechanism, thus influencing the overall ligand-dependent contributions. As for complexes containing Cd and Hg, the ligand-dependent contributions exhibit similar magnitudes when nitrogen is substituted with phosphorus. The only discrepancy arises from the (Formula presented.) contribution, which changes sign between the two molecules due to the contribution of bond orbitals between the metal and tellurium atoms.
Fil: Zapata Escobar, Andy Danian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
Fil: Maldonado, Alejandro Fabián. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
Fil: Mendoza Cortes, Jose L.. Michigan State University; Estados Unidos
Fil: Aucar, Gustavo Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
description In this article, we delve into the intricate behavior of electronic mechanisms underlying NMR magnetic shieldings (Formula presented.) in molecules containing heavy atoms, such as cadmium, platinum, and mercury. Specifically, we explore Pt (Formula presented.) (X = F, Cl, Br, I; n = 4, 6) and XCl (Formula presented.) Te (Formula presented.) (Formula presented.) H (Formula presented.) (X = Cd, Hg; Y = N, P) molecular systems. It is known that the leading electronic mechanisms responsible for the relativistic effects on (Formula presented.) are well characterized by the linear response with elimination of small components model (LRESC). In this study, we present the results obtained from the innovative LRESC-Loc model, which offers the same outcomes as the LRESC model but employs localized molecular orbitals (LMOs) instead of canonical MOs. These LMOs provide a chemist’s representation of atomic core, lone pairs, and bonds. The whole set of electronic mechanisms responsible of the relativistic effects can be expressed in terms of both non-ligand-dependent and ligand-dependent contributions. We elucidate the electronic origins of trends and behaviors exhibited by these diverse mechanisms in the aforementioned molecular systems. In Pt (Formula presented.) molecules, the predominant relativistic mechanism is the well-established one-body spin–orbit ((Formula presented.)) mechanism, while the paramagnetic mass–velocity ((Formula presented.)) and Darwin ((Formula presented.)) contributing mechanisms also demand consideration. However, in Pt (Formula presented.) molecules, the (Formula presented.) contribution surpasses that of the (Formula presented.) mechanism, thus influencing the overall ligand-dependent contributions. As for complexes containing Cd and Hg, the ligand-dependent contributions exhibit similar magnitudes when nitrogen is substituted with phosphorus. The only discrepancy arises from the (Formula presented.) contribution, which changes sign between the two molecules due to the contribution of bond orbitals between the metal and tellurium atoms.
publishDate 2023
dc.date.none.fl_str_mv 2023-06-27
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/235959
Zapata Escobar, Andy Danian; Maldonado, Alejandro Fabián; Mendoza Cortes, Jose L.; Aucar, Gustavo Adolfo; NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and Mercury; Multidisciplinary Digital Publishing Institute; Magnetochemistry; 9; 7; 27-6-2023; 1-15
2312-7481
CONICET Digital
CONICET
url http://hdl.handle.net/11336/235959
identifier_str_mv Zapata Escobar, Andy Danian; Maldonado, Alejandro Fabián; Mendoza Cortes, Jose L.; Aucar, Gustavo Adolfo; NMR Magnetic Shielding in Transition Metal Compounds Containing Cadmium, Platinum, and Mercury; Multidisciplinary Digital Publishing Institute; Magnetochemistry; 9; 7; 27-6-2023; 1-15
2312-7481
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/2312-7481/9/7/165
info:eu-repo/semantics/altIdentifier/doi/10.3390/magnetochemistry9070165
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Multidisciplinary Digital Publishing Institute
publisher.none.fl_str_mv Multidisciplinary Digital Publishing Institute
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.22299

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