A study of aromatic three membered rings

The resonance energies (REs) of neutral three membered ring analogs of the cyclopropenyl cation, computed using block localized wave function (BLW) methods, reveal considerable variations. The RE's of cyclopropenes substituted with exocyclic double bonded groups C?X, (X = O, NH, CH₂, S, PH, SiH₂) increase with the electronegativity of X in the same row (SiH₂ < PH < S and CH₂ < NH < O). The extra cyclic resonance energies (ECREs) (an energetic measure of aromaticity based on comparisons with the RE's of acyclic models) of these derivatives range from +10.5 kcal/mol for cyclopropenone (X = O) (somewhat aromatic; the benzene ECRE is 29.3 kcal/mol) to ?2.4 kcal/mol (slightly antiaromatic) for X = SiH₂. Additional disubstitution of the C?C double bond by X′ groups (X′ = CH₃, NH₂, OH, SiH₃, PH₂, SH) increases the REs considerably, but has only small effects on the ECREs. Even the ECRE of deltic acid (X = O, X′ = OH) is only increased to +13.3 kcal/mol. The conclusion based on ECRE's, that all 12 of the three membered rings are only marginally aromatic/antiaromatic, is supported by the satisfactorily plot (R² = 0.92) of ECRE against values of NICS(0)_πzz (a superior nucleus chemical independent shift magnetic index of aromaticity), which range only from ?6.1 ppm (diatropic) for deltic acid (cf., ?35.5 ppm for benzene and ?14.2 ppm for the parent cyclopropenium ion) to +8.9 ppm (paratropic) for the silicon derivative, X = SiH₂, X′ = SiH₃. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011