Aromaticity in Group 14 homologues of the cyclopropenylium cation

The nature of the bonding and the aromaticity of the heavy Group 14 homologues of cyclopropenylium cations E₃H₃⁺ and E₂H₂E′H⁺ (E, E′=C–Pb) have been investigated systematically at the BP86/TZ2P DFT level by using several methods. Aromatic stabilization energies (ASE) were evaluated from the values obtained from energy decomposition analysis (EDA) of charged acyclic reference molecules. The EDA‐ASE results compare well with the extra cyclic resonance energy (ECRE) values given by the block localized wavefunction (BLW) method. Although all compounds investigated are Hückel 4n+2 π electron species, their ASEs indicate that the inclusion of Group 14 elements heavier than carbon reduces the aromaticity; the parent C₃H₃⁺ ion and Si₂H₂CH⁺ are the most aromatic, and Pb₃H₃⁺ is the least so. The higher energies for the cyclopropenium analogues reported in 1995 employed an isodesmic scheme, and are reinterpreted by using the BLW method. The decrease in the strength of both the π cyclic conjugation and the aromaticity in the order C?Si>Ge>Sn>Pb agrees reasonably well with the trends given by the refined nucleus‐independent chemical shift NICS(0)_πzz index.