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

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 neighbo...

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Autores principales: Passaglia, Lucas, Zanardi, María M., Sarotti, Ariel M.
Formato: Artículo
Lenguaje:Inglés
Publicado: Royal Society of Chemistry 2024
Materias:
EFECTO ATOMO PESADO
BROMURO
CLORURO
DP4+
Acceso en línea:https://repositorio.uca.edu.ar/handle/123456789/19101
Aporte de:
Repositorio Institucional de la Universidad Católica Argentina (UCA) de Universidad Católica Argentina
id I33-R139-123456789-19101
record_format dspace
spelling I33-R139-123456789-191012024-11-27T05:02:22Z Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trends Passaglia, Lucas Zanardi, María M. Sarotti, Ariel M. EFECTO ATOMO PESADO BROMURO CLORURO DP4+ 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. 2024-11-26T12:08:36Z 2024-11-26T12:08:36Z 2024 Artículo 1477-0520 (impreso) 1477-0539 (online) https://repositorio.uca.edu.ar/handle/123456789/19101 10.1039/d3ob02077k eng Atribución-NoComercial-CompartirIgual 4.0 Internacional http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Royal Society of Chemistry Organic & biomolecular chemistry. 2024, 22 (12)
institution Universidad Católica Argentina
institution_str I-33
repository_str R-139
collection Repositorio Institucional de la Universidad Católica Argentina (UCA)
language Inglés
topic EFECTO ATOMO PESADO
BROMURO
CLORURO
DP4+
spellingShingle EFECTO ATOMO PESADO
BROMURO
CLORURO
DP4+
Passaglia, Lucas
Zanardi, María M.
Sarotti, Ariel M.
Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trends
topic_facet EFECTO ATOMO PESADO
BROMURO
CLORURO
DP4+
description 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.
format Artículo
author Passaglia, Lucas
Zanardi, María M.
Sarotti, Ariel M.
author_facet Passaglia, Lucas
Zanardi, María M.
Sarotti, Ariel M.
author_sort Passaglia, Lucas
title Study of heavy atom influence on polyhalogenated compounds using DP4/MM-DP4+/ DP4+: insights and trends
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
publisher Royal Society of Chemistry
publishDate 2024
url https://repositorio.uca.edu.ar/handle/123456789/19101
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AT zanardimariam studyofheavyatominfluenceonpolyhalogenatedcompoundsusingdp4mmdp4dp4insightsandtrends
AT sarottiarielm studyofheavyatominfluenceonpolyhalogenatedcompoundsusingdp4mmdp4dp4insightsandtrends
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