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.

Conformational analysis of 2-trichloromethyl(ethoxycarbonyl)-1-nitro-and 2-trichloromethyl-(ethoxycarbonyl)-1-bromo-1-nitroethenes was performed using the dipole moment method, IR spectroscopy, and DFT quantum-chemical calculations (B3LYP/6-31G*). The nitro and ester (or trichloromethyl) groups in the molecules of these compounds were found to occupy trans positions with respect to the double C=C bond, i.e., the nitroalkenes have E, and their bromine-containing analogs, Z configuration; the compounds having an ethoxycarbonyl group are characterized by s-cis orientation of the C=C and C=O bonds.