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
- Institución
- Pontificia Universidad Católica Argentina
- OAI Identificador
- oai:ucacris:123456789/19101
Ver los metadatos del registro completo
id |
RIUCA_9fcf94ec6af8483d06f0d87f2beaf4ca |
---|---|
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 |
_version_ |
1836638375625359360 |
score |
12.982451 |