Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trends

Autores
Passaglia, Lucas; Zanardi, María M.; Sarotti, Ariel M.
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Fil: Passaglia, Lucas. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Passaglia, Lucas. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; Argentina
Fil: Zanardi, María M. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; Argentina
Fil: Sarotti, Ariel M. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Nuclear magnetic resonance (NMR) spectroscopy complemented by density functional theory (DFT) calculations is a crucial tool for structural elucidation. Nevertheless, the precision of NMR predictions is influenced by the ‘heavy atom effect’, wherein heavy atoms affect the shielding values of neighboring light atoms (HALA effect). Standard practice in the field involves removing the conflicting signals. However, in the case of polyhalogenated molecules, this is challenging due to the significant amount of information that ends up being lost. In this study the HALA is thoroughly investigated in the context of three leading probability methods: DP4, MM-DP4+, and DP4+. The results show that DP4+ is more sensitive to C–Cl or C–Br signals, which is a consequence of the longer bond lengths computed with DFT. Removing conflicting signals is highly effective in DP4+, but has an uncertain outcome in methods based on molecular mechanics geometries, such as DP4 and MM-DP4+. A detailed investigation of the effect of bond distance on the corresponding chemical shifts has also been conducted.
Fuente
Organic & biomolecular chemistry. 2024, 22 (12)
Materia
EFECTO ATOMO PESADO
BROMURO
CLORURO
DP4+
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
Repositorio Institucional (UCA)
Institución
Pontificia Universidad Católica Argentina
OAI Identificador
oai:ucacris:123456789/19101

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oai_identifier_str oai:ucacris:123456789/19101
network_acronym_str RIUCA
repository_id_str 2585
network_name_str Repositorio Institucional (UCA)
spelling Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trendsPassaglia, LucasZanardi, María M.Sarotti, Ariel M.EFECTO ATOMO PESADOBROMUROCLORURODP4+Fil: Passaglia, Lucas. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Passaglia, Lucas. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; ArgentinaFil: Zanardi, María M. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; ArgentinaFil: Sarotti, Ariel M. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaNuclear magnetic resonance (NMR) spectroscopy complemented by density functional theory (DFT) calculations is a crucial tool for structural elucidation. Nevertheless, the precision of NMR predictions is influenced by the ‘heavy atom effect’, wherein heavy atoms affect the shielding values of neighboring light atoms (HALA effect). Standard practice in the field involves removing the conflicting signals. However, in the case of polyhalogenated molecules, this is challenging due to the significant amount of information that ends up being lost. In this study the HALA is thoroughly investigated in the context of three leading probability methods: DP4, MM-DP4+, and DP4+. The results show that DP4+ is more sensitive to C–Cl or C–Br signals, which is a consequence of the longer bond lengths computed with DFT. Removing conflicting signals is highly effective in DP4+, but has an uncertain outcome in methods based on molecular mechanics geometries, such as DP4 and MM-DP4+. A detailed investigation of the effect of bond distance on the corresponding chemical shifts has also been conducted.Royal Society of Chemistry2024info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfhttps://repositorio.uca.edu.ar/handle/123456789/191011477-0520 (impreso)1477-0539 (online)10.1039/d3ob02077kOrganic & biomolecular chemistry. 2024, 22 (12)reponame:Repositorio Institucional (UCA)instname:Pontificia Universidad Católica Argentinaenginfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/4.0/2025-07-03T11:00:03Zoai:ucacris:123456789/19101instacron:UCAInstitucionalhttps://repositorio.uca.edu.ar/Universidad privadaNo correspondehttps://repositorio.uca.edu.ar/oaiclaudia_fernandez@uca.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:25852025-07-03 11:00:03.932Repositorio Institucional (UCA) - Pontificia Universidad Católica Argentinafalse
dc.title.none.fl_str_mv Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trends
title Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trends
spellingShingle Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trends
Passaglia, Lucas
EFECTO ATOMO PESADO
BROMURO
CLORURO
DP4+
title_short Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trends
title_full Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trends
title_fullStr Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trends
title_full_unstemmed Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trends
title_sort Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trends
dc.creator.none.fl_str_mv Passaglia, Lucas
Zanardi, María M.
Sarotti, Ariel M.
author Passaglia, Lucas
author_facet Passaglia, Lucas
Zanardi, María M.
Sarotti, Ariel M.
author_role author
author2 Zanardi, María M.
Sarotti, Ariel M.
author2_role author
author
dc.subject.none.fl_str_mv EFECTO ATOMO PESADO
BROMURO
CLORURO
DP4+
topic EFECTO ATOMO PESADO
BROMURO
CLORURO
DP4+
dc.description.none.fl_txt_mv Fil: Passaglia, Lucas. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Passaglia, Lucas. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; Argentina
Fil: Zanardi, María M. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; Argentina
Fil: Sarotti, Ariel M. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Nuclear magnetic resonance (NMR) spectroscopy complemented by density functional theory (DFT) calculations is a crucial tool for structural elucidation. Nevertheless, the precision of NMR predictions is influenced by the ‘heavy atom effect’, wherein heavy atoms affect the shielding values of neighboring light atoms (HALA effect). Standard practice in the field involves removing the conflicting signals. However, in the case of polyhalogenated molecules, this is challenging due to the significant amount of information that ends up being lost. In this study the HALA is thoroughly investigated in the context of three leading probability methods: DP4, MM-DP4+, and DP4+. The results show that DP4+ is more sensitive to C–Cl or C–Br signals, which is a consequence of the longer bond lengths computed with DFT. Removing conflicting signals is highly effective in DP4+, but has an uncertain outcome in methods based on molecular mechanics geometries, such as DP4 and MM-DP4+. A detailed investigation of the effect of bond distance on the corresponding chemical shifts has also been conducted.
description Fil: Passaglia, Lucas. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
publishDate 2024
dc.date.none.fl_str_mv 2024
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 https://repositorio.uca.edu.ar/handle/123456789/19101
1477-0520 (impreso)
1477-0539 (online)
10.1039/d3ob02077k
url https://repositorio.uca.edu.ar/handle/123456789/19101
identifier_str_mv 1477-0520 (impreso)
1477-0539 (online)
10.1039/d3ob02077k
dc.language.none.fl_str_mv eng
language eng
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/4.0/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/4.0/
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv Organic & biomolecular chemistry. 2024, 22 (12)
reponame:Repositorio Institucional (UCA)
instname:Pontificia Universidad Católica Argentina
reponame_str Repositorio Institucional (UCA)
collection Repositorio Institucional (UCA)
instname_str Pontificia Universidad Católica Argentina
repository.name.fl_str_mv Repositorio Institucional (UCA) - Pontificia Universidad Católica Argentina
repository.mail.fl_str_mv claudia_fernandez@uca.edu.ar
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score 12.982451