Hyperaromatic stabilization of arenium ions |
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Authors: | Kudavalli Jaya S Boyd Derek R Coyne Dara Keeffe James R Lawlor David A MacCormac Aoife C More O'Ferrall Rory A Rao S Nagaraja Sharma Narain D |
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Institution: | School of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland. |
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Abstract: | Benzene-cis- and trans-1,2-dihydrodiols undergo acid-catalyzed dehydration at remarkably different rates: k(cis)/k(trans) = 4500. This is explained by formation of a β-hydroxycarbocation intermediate in different initial conformations, one of which is stabilized by hyperconjugation amplified by an aromatic no-bond resonance structure (HOC(6)H(6)(+) ? HOC(6)H(5) H(+)). MP2 calculations and an unfavorable effect of benzoannelation on benzenium ion stability, implied by pK(R) measurements of -2.3, -8.0, and -11.9 for benzenium, 1-naphthalenium, and 9-phenanthrenium ions, respectively, support the explanation. |
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