Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study
The effects of Lewis basicity and acidity on σ-hole interactions were investigated using two sets of carbon-containing complexes. In Set I, the effect of Lewis basicity was studied by substituting the X<sub>3</sub>/X atom(s) of the NC-C<sub>6</sub>H<sub>2</sub>-X&...
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| Format: | Article |
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MDPI AG
2022-10-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/23/21/13023 |
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| author | Mahmoud A. A. Ibrahim Mohammed N. I. Shehata Al-shimaa S. M. Rady Hassan A. A. Abuelliel Heba S. M. Abd Elhafez Ahmed M. Shawky Hesham Farouk Oraby Tamer H. A. Hasanin Mahmoud E. S. Soliman Nayra A. M. Moussa |
| author_facet | Mahmoud A. A. Ibrahim Mohammed N. I. Shehata Al-shimaa S. M. Rady Hassan A. A. Abuelliel Heba S. M. Abd Elhafez Ahmed M. Shawky Hesham Farouk Oraby Tamer H. A. Hasanin Mahmoud E. S. Soliman Nayra A. M. Moussa |
| author_sort | Mahmoud A. A. Ibrahim |
| collection | DOAJ |
| description | The effects of Lewis basicity and acidity on σ-hole interactions were investigated using two sets of carbon-containing complexes. In Set I, the effect of Lewis basicity was studied by substituting the X<sub>3</sub>/X atom(s) of the NC-C<sub>6</sub>H<sub>2</sub>-X<sub>3</sub> and NCX Lewis bases (LB) with F, Cl, Br, or I. In Set II, the W-C-F<sub>3</sub> and F-C-X<sub>3</sub> (where X and W = F, Cl, Br, and I) molecules were utilized as Lewis acid (LA) centers. Concerning the Lewis basicity effect, higher negative interaction energies (<i>E</i><sub>int</sub>) were observed for the F-C-F<sub>3</sub>∙∙∙NC-C<sub>6</sub>H<sub>2</sub>-X<sub>3</sub> complexes compared with the F-C-F<sub>3</sub>∙∙∙NCX analogs. Moreover, significant <i>E</i><sub>int</sub> was recorded for Set I complexes, along with decreasing the electron-withdrawing power of the X<sub>3</sub>/X atom(s). Among Set I complexes, the highest negative <i>E</i><sub>int</sub> was ascribed to the F-C-F<sub>3</sub>∙∙∙NC-C<sub>6</sub>H<sub>2</sub>-I<sub>3</sub> complex with a value of −1.23 kcal/mol. For Set II complexes, <i>E</i><sub>int</sub> values of F-C-X<sub>3</sub> bearing complexes were noted within the −1.05 to −2.08 kcal/mol scope, while they ranged from −0.82 to −1.20 kcal/mol for the W-C-F<sub>3</sub> analogs. However, <i>V</i><sub>s,max</sub> quantities exhibited higher values in the case of W-C-F<sub>3</sub> molecules compared with F-C-X<sub>3</sub>; preferable negative <i>E</i><sub>int</sub> were ascribed to the F-C-X<sub>3</sub> bearing complexes. These findings were delineated as a consequence of the promoted contributions of the X<sub>3</sub> substituents. Dispersion forces (<i>E</i><sub>disp</sub>) were identified as the dominant forces for these interactions. The obtained results provide a foundation for fields such as crystal engineering and supramolecular chemistry studies that focus on understanding the characteristics of carbon-bearing complexes. |
| first_indexed | 2024-03-09T19:01:44Z |
| format | Article |
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| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-09T19:01:44Z |
| publishDate | 2022-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-87a1516d46904598b42da0509d32d9d62023-11-24T05:01:07ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672022-10-0123211302310.3390/ijms232113023Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio StudyMahmoud A. A. Ibrahim0Mohammed N. I. Shehata1Al-shimaa S. M. Rady2Hassan A. A. Abuelliel3Heba S. M. Abd Elhafez4Ahmed M. Shawky5Hesham Farouk Oraby6Tamer H. A. Hasanin7Mahmoud E. S. Soliman8Nayra A. M. Moussa9Computational Chemistry Laboratory, Chemistry Department, Faculty of Science, Minia University, Minia 61519, EgyptComputational Chemistry Laboratory, Chemistry Department, Faculty of Science, Minia University, Minia 61519, EgyptComputational Chemistry Laboratory, Chemistry Department, Faculty of Science, Minia University, Minia 61519, EgyptComputational Chemistry Laboratory, Chemistry Department, Faculty of Science, Minia University, Minia 61519, EgyptComputational Chemistry Laboratory, Chemistry Department, Faculty of Science, Minia University, Minia 61519, EgyptScience and Technology Unit (STU), Umm Al-Qura University, Makkah 21955, Saudi ArabiaDeanship of Scientific Research, Umm Al-Qura University, Makkah 21955, Saudi ArabiaDepartment of Chemistry, College of Science, Jouf University, Sakaka P.O. Box 2014, Saudi ArabiaMolecular Bio-Computation and Drug Design Research Laboratory, School of Health Sciences, University of Kwa-Zulu-Natal, Westville, Durban 4000, South AfricaComputational Chemistry Laboratory, Chemistry Department, Faculty of Science, Minia University, Minia 61519, EgyptThe effects of Lewis basicity and acidity on σ-hole interactions were investigated using two sets of carbon-containing complexes. In Set I, the effect of Lewis basicity was studied by substituting the X<sub>3</sub>/X atom(s) of the NC-C<sub>6</sub>H<sub>2</sub>-X<sub>3</sub> and NCX Lewis bases (LB) with F, Cl, Br, or I. In Set II, the W-C-F<sub>3</sub> and F-C-X<sub>3</sub> (where X and W = F, Cl, Br, and I) molecules were utilized as Lewis acid (LA) centers. Concerning the Lewis basicity effect, higher negative interaction energies (<i>E</i><sub>int</sub>) were observed for the F-C-F<sub>3</sub>∙∙∙NC-C<sub>6</sub>H<sub>2</sub>-X<sub>3</sub> complexes compared with the F-C-F<sub>3</sub>∙∙∙NCX analogs. Moreover, significant <i>E</i><sub>int</sub> was recorded for Set I complexes, along with decreasing the electron-withdrawing power of the X<sub>3</sub>/X atom(s). Among Set I complexes, the highest negative <i>E</i><sub>int</sub> was ascribed to the F-C-F<sub>3</sub>∙∙∙NC-C<sub>6</sub>H<sub>2</sub>-I<sub>3</sub> complex with a value of −1.23 kcal/mol. For Set II complexes, <i>E</i><sub>int</sub> values of F-C-X<sub>3</sub> bearing complexes were noted within the −1.05 to −2.08 kcal/mol scope, while they ranged from −0.82 to −1.20 kcal/mol for the W-C-F<sub>3</sub> analogs. However, <i>V</i><sub>s,max</sub> quantities exhibited higher values in the case of W-C-F<sub>3</sub> molecules compared with F-C-X<sub>3</sub>; preferable negative <i>E</i><sub>int</sub> were ascribed to the F-C-X<sub>3</sub> bearing complexes. These findings were delineated as a consequence of the promoted contributions of the X<sub>3</sub> substituents. Dispersion forces (<i>E</i><sub>disp</sub>) were identified as the dominant forces for these interactions. The obtained results provide a foundation for fields such as crystal engineering and supramolecular chemistry studies that focus on understanding the characteristics of carbon-bearing complexes.https://www.mdpi.com/1422-0067/23/21/13023σ-hole interactionstetrel bonding interactionsLewis basicityLewis acidityab initio calculations |
| spellingShingle | Mahmoud A. A. Ibrahim Mohammed N. I. Shehata Al-shimaa S. M. Rady Hassan A. A. Abuelliel Heba S. M. Abd Elhafez Ahmed M. Shawky Hesham Farouk Oraby Tamer H. A. Hasanin Mahmoud E. S. Soliman Nayra A. M. Moussa Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study International Journal of Molecular Sciences σ-hole interactions tetrel bonding interactions Lewis basicity Lewis acidity ab initio calculations |
| title | Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study |
| title_full | Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study |
| title_fullStr | Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study |
| title_full_unstemmed | Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study |
| title_short | Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study |
| title_sort | effects of lewis basicity and acidity on σ hole interactions in carbon bearing complexes a comparative ab initio study |
| topic | σ-hole interactions tetrel bonding interactions Lewis basicity Lewis acidity ab initio calculations |
| url | https://www.mdpi.com/1422-0067/23/21/13023 |
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