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Complexes of CO(2) with the Azoles: Tetrel Bonds, Hydrogen Bonds and Other Secondary Interactions
Ab initio MP2/aug’-cc-pVTZ calculations have been performed to investigate the complexes of CO(2) with the azoles pyrrole, pyrazole, imidazole, 1,2,3- and 1,2,4-triazole, tetrazole and pentazole. Three types of complexes have been found on the CO(2):azole potential surfaces. These include ten comple...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2018
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6017967/ https://www.ncbi.nlm.nih.gov/pubmed/29662005 http://dx.doi.org/10.3390/molecules23040906 |
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author | Del Bene, Janet E. Elguero, José Alkorta, Ibon |
author_facet | Del Bene, Janet E. Elguero, José Alkorta, Ibon |
author_sort | Del Bene, Janet E. |
collection | PubMed |
description | Ab initio MP2/aug’-cc-pVTZ calculations have been performed to investigate the complexes of CO(2) with the azoles pyrrole, pyrazole, imidazole, 1,2,3- and 1,2,4-triazole, tetrazole and pentazole. Three types of complexes have been found on the CO(2):azole potential surfaces. These include ten complexes stabilized by tetrel bonds that have the azole molecule in the symmetry plane of the complex; seven tetrel-bonded complexes in which the CO(2) molecule is perpendicular to the symmetry plane; and four hydrogen-bonded complexes. Eight of the planar complexes are stabilized by Nx···C tetrel bonds and by a secondary interaction involving an adjacent Ny-H bond and an O atom of CO(2). The seven perpendicular CO(2):azole complexes form between CO(2) and two adjacent N atoms of the ring, both of which are electron-pair donors. In three of the four hydrogen-bonded complexes, the proton-donor Nz-H bond of the ring is bonded to two C-H bonds, thereby precluding the planar and perpendicular complexes. The fourth hydrogen-bonded complex forms with the strongest acid pentazole. Binding energies, charge-transfer energies and changes in CO(2) stretching and bending frequencies upon complex formation provide consistent descriptions of these complexes. Coupling constants across tetrel bonds are negligibly small, but (2h)J(Ny-C) across Nz-H···C hydrogen bonds are larger and increase as the number of N atoms in the ring increases. |
format | Online Article Text |
id | pubmed-6017967 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-60179672018-11-13 Complexes of CO(2) with the Azoles: Tetrel Bonds, Hydrogen Bonds and Other Secondary Interactions Del Bene, Janet E. Elguero, José Alkorta, Ibon Molecules Article Ab initio MP2/aug’-cc-pVTZ calculations have been performed to investigate the complexes of CO(2) with the azoles pyrrole, pyrazole, imidazole, 1,2,3- and 1,2,4-triazole, tetrazole and pentazole. Three types of complexes have been found on the CO(2):azole potential surfaces. These include ten complexes stabilized by tetrel bonds that have the azole molecule in the symmetry plane of the complex; seven tetrel-bonded complexes in which the CO(2) molecule is perpendicular to the symmetry plane; and four hydrogen-bonded complexes. Eight of the planar complexes are stabilized by Nx···C tetrel bonds and by a secondary interaction involving an adjacent Ny-H bond and an O atom of CO(2). The seven perpendicular CO(2):azole complexes form between CO(2) and two adjacent N atoms of the ring, both of which are electron-pair donors. In three of the four hydrogen-bonded complexes, the proton-donor Nz-H bond of the ring is bonded to two C-H bonds, thereby precluding the planar and perpendicular complexes. The fourth hydrogen-bonded complex forms with the strongest acid pentazole. Binding energies, charge-transfer energies and changes in CO(2) stretching and bending frequencies upon complex formation provide consistent descriptions of these complexes. Coupling constants across tetrel bonds are negligibly small, but (2h)J(Ny-C) across Nz-H···C hydrogen bonds are larger and increase as the number of N atoms in the ring increases. MDPI 2018-04-14 /pmc/articles/PMC6017967/ /pubmed/29662005 http://dx.doi.org/10.3390/molecules23040906 Text en © 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Del Bene, Janet E. Elguero, José Alkorta, Ibon Complexes of CO(2) with the Azoles: Tetrel Bonds, Hydrogen Bonds and Other Secondary Interactions |
title | Complexes of CO(2) with the Azoles: Tetrel Bonds, Hydrogen Bonds and Other Secondary Interactions |
title_full | Complexes of CO(2) with the Azoles: Tetrel Bonds, Hydrogen Bonds and Other Secondary Interactions |
title_fullStr | Complexes of CO(2) with the Azoles: Tetrel Bonds, Hydrogen Bonds and Other Secondary Interactions |
title_full_unstemmed | Complexes of CO(2) with the Azoles: Tetrel Bonds, Hydrogen Bonds and Other Secondary Interactions |
title_short | Complexes of CO(2) with the Azoles: Tetrel Bonds, Hydrogen Bonds and Other Secondary Interactions |
title_sort | complexes of co(2) with the azoles: tetrel bonds, hydrogen bonds and other secondary interactions |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6017967/ https://www.ncbi.nlm.nih.gov/pubmed/29662005 http://dx.doi.org/10.3390/molecules23040906 |
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