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Hyperaromatic Stabilization of Arenium Ions: Cyclohexa- and Cycloheptadienyl CationsExperimental and Calculated Stabilities and Ring Currents

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journal contribution
posted on 14.12.2011, 00:00 by David A. Lawlor, David E. Bean, Patrick W. Fowler, James R. Keeffe, Jaya Satyanarayana Kudavalli, Rory A. More O’Ferrall, S. Nagaraja Rao
Measurements of pKR show that the cycloheptadienyl cation is less stable than the cyclohexadienyl (benzenium) cation by 18 kcal mol–1. This difference is ascribed here to “hyperaromaticity” of the latter. For the cycloheptadienyl cation a value of KR = [ROH][H+]/[R+] is assigned by combining a rate constant for reaction of the cation with water based on the azide clock with a rate constant for the acid-catalyzed formation of the cation accompanying equilibration of cycloheptadienol with its trifluoroethyl ether in TFE–water mixtures. Comparison of pKR = −16.1 with pKR = −2.6 for the cyclohexadienyl cation yields the difference in stabilities of the two ions. Interpretation of this difference in terms of hyperconjugative aromaticity is supported by the effect of benzannelation in reducing pKR for the benzenium ion: from −2.6 down to −3.5 for the 1H-naphthalenium and −6.0 for the 9H-anthracenium ions, respectively. MP2/6-311+G** and G3MP2 calculations of hydride ion affinities of benzenium ions show an order of stabilities for substituents at the methylene group consistent with their hyperconjugative abilities, i.e., (H3Si)2 > cyclopropyl > H2 > Me2> (HO)2 > F2. Calculations of ring currents show a similar ordering. No conventional ring current is seen for the cycloheptadienyl cation, whereas currents in the F2-substituted benzenium ion are consistent with antiaromaticity. Arenium ions where the methylene group is substituted with a single OH group show characteristic energy differences between conformations, with C–H or C–OH bonds respectively occupying or constrained to axial positions favorable to hyperconjugation. The differences were found to be 8.8, 6.3, 2.4, and 0.4 kcal mol–1 for benzenium, naphthalenium, phenanthrenium, and cyclohexenyl cations, respectively.