The Effect of Intramolecular Hydrogen Bond Type on the Gas-Phase Deprotonation of <i>ortho</i>-Substituted Benzenesulfonic Acids. A Density Functional Theory Study
Structural factors have been identified that determine the gas-phase acidity of <i>ortho</i>-substituted benzenesulfonic acid, 2-XC<sub>6</sub>H<sub>4</sub>–SO<sub>3</sub>H, (X = –SO<sub>3</sub>H, –COOH, –NO<sub>2</sub>, –SO<...
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MDPI AG
2020-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/24/5806 |
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| author | Nina I. Giricheva Sergey N. Ivanov Anastasiya V. Ignatova Mikhail S. Fedorov Georgiy V. Girichev |
| author_facet | Nina I. Giricheva Sergey N. Ivanov Anastasiya V. Ignatova Mikhail S. Fedorov Georgiy V. Girichev |
| author_sort | Nina I. Giricheva |
| collection | DOAJ |
| description | Structural factors have been identified that determine the gas-phase acidity of <i>ortho</i>-substituted benzenesulfonic acid, 2-XC<sub>6</sub>H<sub>4</sub>–SO<sub>3</sub>H, (X = –SO<sub>3</sub>H, –COOH, –NO<sub>2</sub>, –SO<sub>2</sub>F, –C≡N, –NH<sub>2</sub>, –CH<sub>3</sub>, –OCH<sub>3</sub>, –N(CH<sub>3</sub>)<sub>2</sub>, –OH). The DFT/B3LYP/cc-pVTZ method was used to perform conformational analysis and study the structural features of the molecular and deprotonated forms of these compounds. It has been shown that many of the conformers may contain anintramolecular hydrogen bond (IHB) between the sulfonic group and the substituent, and the sulfonic group can be an IHB donor or an acceptor. The Gibbs energies of gas-phase deprotonation Δ<sub>r</sub>G<sup>0</sup><sub>298</sub> (kJ mol<sup>–1</sup>) were calculated for all compounds. It has been set that in <i>ortho</i>-substituted benzenesulfonic acids, the formation of various types of IHB is possible, having a significant effect on the Δ<sub>r</sub>G<sup>0</sup><sub>298</sub> values of gas-phase deprotonation. If the –SO<sub>3</sub>H group is the IHB donor, then an ion without an IHB is formed upon deprotonation, and the deprotonation energy increases. If this group is an IHB acceptor, then a significant decrease in Δ<sub>r</sub>G<sup>0</sup><sub>298</sub> of gas-phase deprotonation is observed due to an increase in IHB strength and the A<sup>−</sup> anion additional stabilization. A proton donor ability comparative characteristic of the –SO<sub>3</sub>H group in the studied <i>ortho</i>-substituted benzenesulfonic acids is given, and the Δ<sub>r</sub>G<sup>0</sup><sub>298</sub> energies are compared with the corresponding values of <i>ortho</i>-substituted benzoic acids. |
| first_indexed | 2024-03-10T14:14:03Z |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
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| last_indexed | 2024-03-10T14:14:03Z |
| publishDate | 2020-12-01 |
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| spelling | doaj.art-dfdad858f5ca457fa6d37cc66e33e71a2023-11-20T23:59:36ZengMDPI AGMolecules1420-30492020-12-012524580610.3390/molecules25245806The Effect of Intramolecular Hydrogen Bond Type on the Gas-Phase Deprotonation of <i>ortho</i>-Substituted Benzenesulfonic Acids. A Density Functional Theory StudyNina I. Giricheva0Sergey N. Ivanov1Anastasiya V. Ignatova2Mikhail S. Fedorov3Georgiy V. Girichev4Department of Fundamental and Applied Chemistry, Ivanovo State University, 153025 Ivanovo, RussiaDepartment of Fundamental and Applied Chemistry, Ivanovo State University, 153025 Ivanovo, RussiaDepartment of Fundamental and Applied Chemistry, Ivanovo State University, 153025 Ivanovo, RussiaDepartment of Fundamental and Applied Chemistry, Ivanovo State University, 153025 Ivanovo, RussiaDepartment of Physics, Ivanovo State University of Chemistry and Technology, 153000 Ivanovo, RussiaStructural factors have been identified that determine the gas-phase acidity of <i>ortho</i>-substituted benzenesulfonic acid, 2-XC<sub>6</sub>H<sub>4</sub>–SO<sub>3</sub>H, (X = –SO<sub>3</sub>H, –COOH, –NO<sub>2</sub>, –SO<sub>2</sub>F, –C≡N, –NH<sub>2</sub>, –CH<sub>3</sub>, –OCH<sub>3</sub>, –N(CH<sub>3</sub>)<sub>2</sub>, –OH). The DFT/B3LYP/cc-pVTZ method was used to perform conformational analysis and study the structural features of the molecular and deprotonated forms of these compounds. It has been shown that many of the conformers may contain anintramolecular hydrogen bond (IHB) between the sulfonic group and the substituent, and the sulfonic group can be an IHB donor or an acceptor. The Gibbs energies of gas-phase deprotonation Δ<sub>r</sub>G<sup>0</sup><sub>298</sub> (kJ mol<sup>–1</sup>) were calculated for all compounds. It has been set that in <i>ortho</i>-substituted benzenesulfonic acids, the formation of various types of IHB is possible, having a significant effect on the Δ<sub>r</sub>G<sup>0</sup><sub>298</sub> values of gas-phase deprotonation. If the –SO<sub>3</sub>H group is the IHB donor, then an ion without an IHB is formed upon deprotonation, and the deprotonation energy increases. If this group is an IHB acceptor, then a significant decrease in Δ<sub>r</sub>G<sup>0</sup><sub>298</sub> of gas-phase deprotonation is observed due to an increase in IHB strength and the A<sup>−</sup> anion additional stabilization. A proton donor ability comparative characteristic of the –SO<sub>3</sub>H group in the studied <i>ortho</i>-substituted benzenesulfonic acids is given, and the Δ<sub>r</sub>G<sup>0</sup><sub>298</sub> energies are compared with the corresponding values of <i>ortho</i>-substituted benzoic acids.https://www.mdpi.com/1420-3049/25/24/5806benzenesulfonic acidsconformerdeprotonation energyintramolecular hydrogen bond<i>ortho</i>-effect |
| spellingShingle | Nina I. Giricheva Sergey N. Ivanov Anastasiya V. Ignatova Mikhail S. Fedorov Georgiy V. Girichev The Effect of Intramolecular Hydrogen Bond Type on the Gas-Phase Deprotonation of <i>ortho</i>-Substituted Benzenesulfonic Acids. A Density Functional Theory Study Molecules benzenesulfonic acids conformer deprotonation energy intramolecular hydrogen bond <i>ortho</i>-effect |
| title | The Effect of Intramolecular Hydrogen Bond Type on the Gas-Phase Deprotonation of <i>ortho</i>-Substituted Benzenesulfonic Acids. A Density Functional Theory Study |
| title_full | The Effect of Intramolecular Hydrogen Bond Type on the Gas-Phase Deprotonation of <i>ortho</i>-Substituted Benzenesulfonic Acids. A Density Functional Theory Study |
| title_fullStr | The Effect of Intramolecular Hydrogen Bond Type on the Gas-Phase Deprotonation of <i>ortho</i>-Substituted Benzenesulfonic Acids. A Density Functional Theory Study |
| title_full_unstemmed | The Effect of Intramolecular Hydrogen Bond Type on the Gas-Phase Deprotonation of <i>ortho</i>-Substituted Benzenesulfonic Acids. A Density Functional Theory Study |
| title_short | The Effect of Intramolecular Hydrogen Bond Type on the Gas-Phase Deprotonation of <i>ortho</i>-Substituted Benzenesulfonic Acids. A Density Functional Theory Study |
| title_sort | effect of intramolecular hydrogen bond type on the gas phase deprotonation of i ortho i substituted benzenesulfonic acids a density functional theory study |
| topic | benzenesulfonic acids conformer deprotonation energy intramolecular hydrogen bond <i>ortho</i>-effect |
| url | https://www.mdpi.com/1420-3049/25/24/5806 |
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