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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Bibliographic Details
Published in:Molecules (Basel, Switzerland) Switzerland), 2020-06, Vol.25 (12), p.2803
Main Authors: Chachkov, Denis, Ismagilova, Rezeda, Vereshchagina, Yana
Format: Article
Language:English
Subjects:
Activation energy
Alcohols
atranes
Bonding
Chemical reactions
conformational analysis
Density functional theory
Electronegativity
Energy
Ethanol
Ethanol - chemistry
Germanium
Heterocyclic Compounds - chemistry
Hydrogen bonds
hypoatranes
mechanism of reaction
Methanol - chemistry
Models, Chemical
Nitrogen
ocanes
Quantum Theory
Silicon
Silicon compounds
Studies
Substitutes
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Summary: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.
ISSN:1420-3049
1420-3049
DOI:10.3390/molecules25122803