The aromatic character and resonance stabilization energies of substituted cyclopentadienyl and indenyl cations

Calculations (B3LYP/6-31G(d)) have been used to assess the aromaticity of 5-X substituted indenyl (4) and cyclopentadienyl (5) cations with X = O – , NH 2 , OCH 3 , CH 3 , F, H, CN, and N 2 + . Two criteria were used, the aromatic stabilization energy (ASE), as determined by isodesmic reactions, and bond alternation, as determined from the Julg index (A) on the basis of carbon–carbon bond lengths. Substituent effects on the singlet state of the cyclopentadienyl cations resulted in significant decreases in antiaromatic character for electron-donating groups as indicated by larger A values (A = –0.25 for X = H and +0.26 for X = NH 2 ). These decreases paralleled increases in the C-2—C-3 bond length and good linear correlations were obtained between A vs. the C-2—C-3 bond length and A vs. the ASE. These effects were rationalized by the stabilization by the electron-donating groups of the positive charge at C-5 generated as a consequence of a Jahn–Teller distortion leading to a lowest energy singlet state with a HOMO of a 2 symmetry. In contrast, the lowest energy triplet state for each of the substituted cyclopentadienyl cations has little bond alternation (A > 0.9) and, by this criterion, is not significantly antiaromatic. The triplet state is more stable than the singlet state for the unsubstituted case and those with electron-withdrawing groups (ΔE ST = –11.3 and –9.3 kcal/mol for X = H and CN, respectively) (1 cal = 4.184 J), but less stable for electron-donating groups (ΔE ST = +15.0 kcal/mol for X = NH 2 ). For the indenyl cations 4, the ASE values were almost independent of the substituent and the A values only decreased slightly for electron-donating groups. The A values also indicated that the indenyl cations could be divided into two moieties, an X-substituted pentadienyl cation with considerable delocalization and little bond alternation, and a 2,3-butadiene one with considerable bond alternation. This separation also placed the major portion of the positive charge on the pentadienyl part. The lack of symmetry in the substituted indenyl cations rationalizes the selective reactivity of the 5-methoxy-substituted cation at C-1. Finally, the resonance stabilization energies (RSE) of the substituted cations gave a linear correlation with the RSEs of 4-substituted benzylic cations.Key words: indenyl cations, cyclopentadienyl cations, substituent effects, stabilization energies.

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