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Substituent Effects in Tetrel Bonds Involving Aromatic Silane Derivatives: An ab initio Study
In this manuscript substituent effects in several silicon tetrel bonding (TtB) complexes were investigated at the RI-MP2/def2-TZVP level of theory. Particularly, we have analysed how the interaction energy is influenced by the electronic nature of the substituent in both donor and acceptor moieties....
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10004842/ https://www.ncbi.nlm.nih.gov/pubmed/36903636 http://dx.doi.org/10.3390/molecules28052385 |
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author | Burguera, Sergi Frontera, Antonio Bauzá, Antonio |
author_facet | Burguera, Sergi Frontera, Antonio Bauzá, Antonio |
author_sort | Burguera, Sergi |
collection | PubMed |
description | In this manuscript substituent effects in several silicon tetrel bonding (TtB) complexes were investigated at the RI-MP2/def2-TZVP level of theory. Particularly, we have analysed how the interaction energy is influenced by the electronic nature of the substituent in both donor and acceptor moieties. To achieve that, several tetrafluorophenyl silane derivatives have been substituted at the meta and para positions by several electron donating and electron withdrawing groups (EDG and EWG, respectively), such as –NH(2), –OCH(3), –CH(3), –H, –CF(3) and –CN substituents. As electron donor molecules, we have used a series of hydrogen cyanide derivatives using the same EDGs and EWGs. We have obtained the Hammett’s plots for different combinations of donors and acceptors and in all cases we have obtained good regression plots (interaction energies vs. Hammet’s σ parameter). In addition, we have used the electrostatic potential (ESP) surface analysis as well as the Bader’s theory of atoms in molecules (AIM) and noncovalent interaction plot (NCI plot) techniques to further characterize the TtBs studied herein. Finally, a Cambridge Structural Database (CSD) inspection was carried out, retrieving several structures where halogenated aromatic silanes participate in tetrel bonding interactions, being an additional stabilization force of their supramolecular architectures. |
format | Online Article Text |
id | pubmed-10004842 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-100048422023-03-11 Substituent Effects in Tetrel Bonds Involving Aromatic Silane Derivatives: An ab initio Study Burguera, Sergi Frontera, Antonio Bauzá, Antonio Molecules Article In this manuscript substituent effects in several silicon tetrel bonding (TtB) complexes were investigated at the RI-MP2/def2-TZVP level of theory. Particularly, we have analysed how the interaction energy is influenced by the electronic nature of the substituent in both donor and acceptor moieties. To achieve that, several tetrafluorophenyl silane derivatives have been substituted at the meta and para positions by several electron donating and electron withdrawing groups (EDG and EWG, respectively), such as –NH(2), –OCH(3), –CH(3), –H, –CF(3) and –CN substituents. As electron donor molecules, we have used a series of hydrogen cyanide derivatives using the same EDGs and EWGs. We have obtained the Hammett’s plots for different combinations of donors and acceptors and in all cases we have obtained good regression plots (interaction energies vs. Hammet’s σ parameter). In addition, we have used the electrostatic potential (ESP) surface analysis as well as the Bader’s theory of atoms in molecules (AIM) and noncovalent interaction plot (NCI plot) techniques to further characterize the TtBs studied herein. Finally, a Cambridge Structural Database (CSD) inspection was carried out, retrieving several structures where halogenated aromatic silanes participate in tetrel bonding interactions, being an additional stabilization force of their supramolecular architectures. MDPI 2023-03-05 /pmc/articles/PMC10004842/ /pubmed/36903636 http://dx.doi.org/10.3390/molecules28052385 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/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 (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Burguera, Sergi Frontera, Antonio Bauzá, Antonio Substituent Effects in Tetrel Bonds Involving Aromatic Silane Derivatives: An ab initio Study |
title | Substituent Effects in Tetrel Bonds Involving Aromatic Silane Derivatives: An ab initio Study |
title_full | Substituent Effects in Tetrel Bonds Involving Aromatic Silane Derivatives: An ab initio Study |
title_fullStr | Substituent Effects in Tetrel Bonds Involving Aromatic Silane Derivatives: An ab initio Study |
title_full_unstemmed | Substituent Effects in Tetrel Bonds Involving Aromatic Silane Derivatives: An ab initio Study |
title_short | Substituent Effects in Tetrel Bonds Involving Aromatic Silane Derivatives: An ab initio Study |
title_sort | substituent effects in tetrel bonds involving aromatic silane derivatives: an ab initio study |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10004842/ https://www.ncbi.nlm.nih.gov/pubmed/36903636 http://dx.doi.org/10.3390/molecules28052385 |
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