Mechanism of Reactions of 1-Substituted Silatranes and Germatranes, 2,2-Disubstituted Silocanes and Germocanes, 1,1,1-Trisubstituted Hyposilatranes and Hypogermatranes with Alcohols (Methanol, Ethanol): DFT Study
The mechanism of reactions of silatranes and germatranes, and their bicyclic and monocyclic analogues with one molecule of methanol or ethanol, was studied at the Density Functional Theory (DFT) B3PW91/6-311++G(df,p) level of theory. Reactions of 1-substituted sil(germ)atranes, 2,2-disubstituted sil...
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MDPI AG
2020-06-01
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| Online Access: | https://www.mdpi.com/1420-3049/25/12/2803 |
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| author | Denis Chachkov Rezeda Ismagilova Yana Vereshchagina |
| author_facet | Denis Chachkov Rezeda Ismagilova Yana Vereshchagina |
| author_sort | Denis Chachkov |
| collection | DOAJ |
| description | The mechanism of reactions of silatranes and germatranes, and their bicyclic and monocyclic analogues with one molecule of methanol or ethanol, was studied at the Density Functional Theory (DFT) B3PW91/6-311++G(df,p) level of theory. Reactions of 1-substituted sil(germ)atranes, 2,2-disubstituted sil(germ)ocanes, and 1,1,1-trisubstituted hyposil(germ)atranes with alcohol (methanol, ethanol) proceed in one step through four-center transition states followed by the opening of a silicon or germanium skeleton and the formation of products. According to quantum chemical calculations, the activation energies and Gibbs energies of activation of reactions with methanol and ethanol are close, their values decrease in the series of atranes–ocanes–hypoatranes for interactions with both methanol and ethanol. The reactions of germanium-containing derivatives are characterized by lower activation energies in comparison with the reactions of corresponding silicon-containing compounds. The annular configurations of the product molecules with electronegative substituents are stabilized by the transannular N→X (X = Si, Ge) bond and different intramolecular hydrogen contacts with the participation of heteroatoms of substituents at the silicon or germanium. |
| first_indexed | 2024-03-10T19:05:55Z |
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| id | doaj.art-347b625105c541849a147a81b73dff6d |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T19:05:55Z |
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| spelling | doaj.art-347b625105c541849a147a81b73dff6d2023-11-20T04:08:45ZengMDPI AGMolecules1420-30492020-06-012512280310.3390/molecules25122803Mechanism of Reactions of 1-Substituted Silatranes and Germatranes, 2,2-Disubstituted Silocanes and Germocanes, 1,1,1-Trisubstituted Hyposilatranes and Hypogermatranes with Alcohols (Methanol, Ethanol): DFT StudyDenis Chachkov0Rezeda Ismagilova1Yana Vereshchagina2Kazan Department of Joint Supercomputer Center of Russian Academy of Sciences–Branch of Federal State Institution “Scientific Research Institute for System Analysis of the RAS”, Lobachevskogo 2/31, 420111 Kazan, RussiaDepartment of Physical Chemistry, A.M. Butlerov Institute of Chemistry, Kazan Federal University, Kremlevskaya 18, 420008 Kazan, RussiaDepartment of Physical Chemistry, A.M. Butlerov Institute of Chemistry, Kazan Federal University, Kremlevskaya 18, 420008 Kazan, RussiaThe mechanism of reactions of silatranes and germatranes, and their bicyclic and monocyclic analogues with one molecule of methanol or ethanol, was studied at the Density Functional Theory (DFT) B3PW91/6-311++G(df,p) level of theory. Reactions of 1-substituted sil(germ)atranes, 2,2-disubstituted sil(germ)ocanes, and 1,1,1-trisubstituted hyposil(germ)atranes with alcohol (methanol, ethanol) proceed in one step through four-center transition states followed by the opening of a silicon or germanium skeleton and the formation of products. According to quantum chemical calculations, the activation energies and Gibbs energies of activation of reactions with methanol and ethanol are close, their values decrease in the series of atranes–ocanes–hypoatranes for interactions with both methanol and ethanol. The reactions of germanium-containing derivatives are characterized by lower activation energies in comparison with the reactions of corresponding silicon-containing compounds. The annular configurations of the product molecules with electronegative substituents are stabilized by the transannular N→X (X = Si, Ge) bond and different intramolecular hydrogen contacts with the participation of heteroatoms of substituents at the silicon or germanium.https://www.mdpi.com/1420-3049/25/12/2803atranesocaneshypoatranesconformational analysismechanism of reactionalcohols |
| spellingShingle | Denis Chachkov Rezeda Ismagilova Yana Vereshchagina Mechanism of Reactions of 1-Substituted Silatranes and Germatranes, 2,2-Disubstituted Silocanes and Germocanes, 1,1,1-Trisubstituted Hyposilatranes and Hypogermatranes with Alcohols (Methanol, Ethanol): DFT Study Molecules atranes ocanes hypoatranes conformational analysis mechanism of reaction alcohols |
| title | Mechanism of Reactions of 1-Substituted Silatranes and Germatranes, 2,2-Disubstituted Silocanes and Germocanes, 1,1,1-Trisubstituted Hyposilatranes and Hypogermatranes with Alcohols (Methanol, Ethanol): DFT Study |
| title_full | Mechanism of Reactions of 1-Substituted Silatranes and Germatranes, 2,2-Disubstituted Silocanes and Germocanes, 1,1,1-Trisubstituted Hyposilatranes and Hypogermatranes with Alcohols (Methanol, Ethanol): DFT Study |
| title_fullStr | Mechanism of Reactions of 1-Substituted Silatranes and Germatranes, 2,2-Disubstituted Silocanes and Germocanes, 1,1,1-Trisubstituted Hyposilatranes and Hypogermatranes with Alcohols (Methanol, Ethanol): DFT Study |
| title_full_unstemmed | Mechanism of Reactions of 1-Substituted Silatranes and Germatranes, 2,2-Disubstituted Silocanes and Germocanes, 1,1,1-Trisubstituted Hyposilatranes and Hypogermatranes with Alcohols (Methanol, Ethanol): DFT Study |
| title_short | Mechanism of Reactions of 1-Substituted Silatranes and Germatranes, 2,2-Disubstituted Silocanes and Germocanes, 1,1,1-Trisubstituted Hyposilatranes and Hypogermatranes with Alcohols (Methanol, Ethanol): DFT Study |
| title_sort | mechanism of reactions of 1 substituted silatranes and germatranes 2 2 disubstituted silocanes and germocanes 1 1 1 trisubstituted hyposilatranes and hypogermatranes with alcohols methanol ethanol dft study |
| topic | atranes ocanes hypoatranes conformational analysis mechanism of reaction alcohols |
| url | https://www.mdpi.com/1420-3049/25/12/2803 |
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