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
| Autor: | Rezeda R. Ismagilova, Denis V. Chachkov, Yana A. Vereshchagina |
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| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Heteroatom
Pharmaceutical Science Alcohol hypoatranes DFT calculations Medicinal chemistry Article Analytical Chemistry alcohols lcsh:QD241-441 chemistry.chemical_compound lcsh:Organic chemistry Heterocyclic Compounds Drug Discovery mechanism of reaction Molecule ocanes Physical and Theoretical Chemistry Ethanol Bicyclic molecule Methanol atranes Organic Chemistry conformational analysis Transition state Models Chemical chemistry Chemistry (miscellaneous) Intramolecular force Quantum Theory Molecular Medicine Density functional theory |
| Zdroj: | Molecules, Vol 25, Iss 2803, p 2803 (2020) Molecules Volume 25 Issue 12 |
| ISSN: | 1420-3049 |
| Popis: | 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&ndash ocanes&ndash 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&rarr X (X = Si, Ge) bond and different intramolecular hydrogen contacts with the participation of heteroatoms of substituents at the silicon or germanium. |
| Databáze: | OpenAIRE |
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