<p>Bromosulfonamidation of divinylsilanes involving interception of solvent molecule (acetonitrile) was analyzed theoretically in terms of the density functional theory (DFT). The energies of all intermediates were calculated and the changes of the energy profile of the reaction on going from silanes to their carbon analogues were evaluated. The calculated molecular electrostatic potential (MEP) values in monomeric molecules of reaction products were used as a quantitative measure of the basicity and acidity of the centers involved in the formation of different types of self-associates. The energies of intermolecular hydrogen bonds NH⋯OS, NH⋯N, and CH⋯OS were calculated. The nature of these hydrogen bonding interactions was analyzed in terms of the quantum theory “Atoms in Molecules” (QTAIM). A comparison of the results of calculations and experimental IR spectroscopy data suggests that linear dimers of reaction products provide a basis for the supramolecular structure in the solid phase.</p>