Comparative analysis of equilibrium structures of cations [RM(OCH₂CH₂)₂NCH₃]⁺ (M = Si, Ge; R = F, Me, Ph) and the corresponding neutral compounds HRM(OCH₂CH₂)₂NCH₃ was performed based on quantum-chemical calculations. The possibility was analyzed for expanding nuclear-chemical method to generation of cations having the atrane structure. Quantum-chemical method was applied to estimate the heights of barriers to hydrolysis by the bond in ocanes acting as the sources of the corresponding cations with the atrane structure.