title: Electrophilicities of symmetrically substituted 1,3-diarylallyl cations.
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.
authors.affiliation: Department Chemie, Ludwig-Maximilians-Universität München, 81377 München, Germany.
authors.forename: Konstantin
authors.initials: K
authors.lastname: Troshin
authors.forename: Claus
authors.initials: C
authors.lastname: Schindele
authors.forename: Herbert
authors.initials: H
authors.lastname: Mayr