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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/235959
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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 Técnicas2025-09-29T09:51:08Zoai: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:34982025-09-29 09:51:08.857CONICET 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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13.070432 |