Electrophilicities of symmetrically substituted 1,3-diarylallyl cations |
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Authors: | Troshin Konstantin Schindele Claus Mayr Herbert |
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Affiliation: | Department Chemie, Ludwig-Maximilians-Universit?t München, 81377 München, Germany. |
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Abstract: | Kinetics of the reactions of nine symmetrically substituted 1,3-diarylallyl cations with different nucleophiles were studied photometrically in dichloromethane, acetonitrile, and DMSO solutions. The second-order rate constants k(2) were found to follow the correlation log k(2) = s(N)(N + E). The electrophilicity parameters E of the title cations were derived, using the known values of s(N) and N of the nucleophilic reaction partners, and compared with the electrophilicities of analogously substituted benzhydrylium ions. Good linear correlations were found between the electrophilicities E and the quantum chemically calculated gas-phase methyl anion affinities of the allyl cations and the σ(+) constants of the substituents X. |
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