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Bonding, Aromaticity and Isomerization of Furfuraldehyde through Off‐Nucleus Isotropic Magnetic Shielding
Off‐nucleus isotropic magnetic shielding (σ (iso)(r)) and multi‐points nucleus independent chemical shift (NICS(0‐2 Å)) index were utilized to find the impacts of the isomerization of gas‐phase furfuraldehyde (FD) on bonding and aromaticity of FD. Multidimensional (1D to 3D) grids of ghost atoms (bq...
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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John Wiley and Sons Inc.
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8485829/ https://www.ncbi.nlm.nih.gov/pubmed/34596975 http://dx.doi.org/10.1002/open.202100202 |
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author | Al‐Yassiri, Muntadar A. H. |
author_facet | Al‐Yassiri, Muntadar A. H. |
author_sort | Al‐Yassiri, Muntadar A. H. |
collection | PubMed |
description | Off‐nucleus isotropic magnetic shielding (σ (iso)(r)) and multi‐points nucleus independent chemical shift (NICS(0‐2 Å)) index were utilized to find the impacts of the isomerization of gas‐phase furfuraldehyde (FD) on bonding and aromaticity of FD. Multidimensional (1D to 3D) grids of ghost atoms (bqs) were used as local magnetic probes to evaluate σ (iso)(r) through gauge‐including atomic orbitals (GIAO) at density functional theory (DFT) and B3LYP functional/6‐311+G(d,p) basis set level of theory. 1D σ (iso)(r) responses along each bond of FD were examined. Also, a σ (iso)(r) 2D‐scan was performed to obtain σ (iso)(r) behavior at vertical heights of 0–1 Å above the FD plane in its cis, transition state (TS) and trans forms. New techniques for evaluating 2D σ (iso)(r) cross‐sections are also included. Our findings showed that bonds in cyclic and acyclic parts of FD are dissimilar. Unlike the C−O bond of furanyl, the C=O bond of the formyl group is magnetically different. C−C and C−H bonds in furanyl are found similar to those in aromatic rings. A unique σ (iso)(r) trend was observed for the C(2)−C(6) bond during FD isomerization. Based on NICS(0‐2 Å) values, the degree of aromaticity follows the order of cis FD<trans FD<furan<TS FD. |
format | Online Article Text |
id | pubmed-8485829 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-84858292021-10-06 Bonding, Aromaticity and Isomerization of Furfuraldehyde through Off‐Nucleus Isotropic Magnetic Shielding Al‐Yassiri, Muntadar A. H. ChemistryOpen Full Papers Off‐nucleus isotropic magnetic shielding (σ (iso)(r)) and multi‐points nucleus independent chemical shift (NICS(0‐2 Å)) index were utilized to find the impacts of the isomerization of gas‐phase furfuraldehyde (FD) on bonding and aromaticity of FD. Multidimensional (1D to 3D) grids of ghost atoms (bqs) were used as local magnetic probes to evaluate σ (iso)(r) through gauge‐including atomic orbitals (GIAO) at density functional theory (DFT) and B3LYP functional/6‐311+G(d,p) basis set level of theory. 1D σ (iso)(r) responses along each bond of FD were examined. Also, a σ (iso)(r) 2D‐scan was performed to obtain σ (iso)(r) behavior at vertical heights of 0–1 Å above the FD plane in its cis, transition state (TS) and trans forms. New techniques for evaluating 2D σ (iso)(r) cross‐sections are also included. Our findings showed that bonds in cyclic and acyclic parts of FD are dissimilar. Unlike the C−O bond of furanyl, the C=O bond of the formyl group is magnetically different. C−C and C−H bonds in furanyl are found similar to those in aromatic rings. A unique σ (iso)(r) trend was observed for the C(2)−C(6) bond during FD isomerization. Based on NICS(0‐2 Å) values, the degree of aromaticity follows the order of cis FD<trans FD<furan<TS FD. John Wiley and Sons Inc. 2021-10-01 /pmc/articles/PMC8485829/ /pubmed/34596975 http://dx.doi.org/10.1002/open.202100202 Text en © 2021 The Authors. Published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made. |
spellingShingle | Full Papers Al‐Yassiri, Muntadar A. H. Bonding, Aromaticity and Isomerization of Furfuraldehyde through Off‐Nucleus Isotropic Magnetic Shielding |
title | Bonding, Aromaticity and Isomerization of Furfuraldehyde through Off‐Nucleus Isotropic Magnetic Shielding |
title_full | Bonding, Aromaticity and Isomerization of Furfuraldehyde through Off‐Nucleus Isotropic Magnetic Shielding |
title_fullStr | Bonding, Aromaticity and Isomerization of Furfuraldehyde through Off‐Nucleus Isotropic Magnetic Shielding |
title_full_unstemmed | Bonding, Aromaticity and Isomerization of Furfuraldehyde through Off‐Nucleus Isotropic Magnetic Shielding |
title_short | Bonding, Aromaticity and Isomerization of Furfuraldehyde through Off‐Nucleus Isotropic Magnetic Shielding |
title_sort | bonding, aromaticity and isomerization of furfuraldehyde through off‐nucleus isotropic magnetic shielding |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8485829/ https://www.ncbi.nlm.nih.gov/pubmed/34596975 http://dx.doi.org/10.1002/open.202100202 |
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