title: Reactions of the phthalimide N-oxyl radical (PINO) with activated phenols: the contribution of π-stacking interactions to hydrogen atom transfer rates.
abstract: The kinetics of reactions of the phthalimide N-oxyl radical (PINO) with a series of activated phenols (2,2,5,7,8-pentamethylchroman-6-ol (PMC), 2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols) were investigated by laser flash photolysis in CH(3)CN and PhCl in order to establish if the reactions with PINO can provide a useful tool for evaluating the radical scavenging ability of phenolic antioxidants. On the basis of the small values of deuterium kinetic isotope effects, the relatively high and negative ρ values in the Hammett correlations and the results of theoretical calculations, we suggest that these reactions proceed by a hydrogen atom transfer (HAT) mechanism having a significant degree of charge transfer resulting from a π-stacked conformation between PINO and the aromatic ring of the phenols. Kinetic solvent effects were analyzed in detail for the hydrogen transfer from 2,4,6-trimethylphenol to PINO and the data obtained are in accordance with the Snelgrove-Ingold equation for HAT. Experimental rate constants for the reactions of PINO with activated phenols are in accordance with those predicted by applying the Marcus cross relation.
authors.affiliation: Dipartimento di Chimica, Sapienza Università di Roma and Istituto CNR di Metodologie Chimiche (IMC-CNR), Sezione Meccanismi di Reazione, P.le A. Moro, 5 I-00185 Rome, Italy.
authors.forename: Claudio
authors.initials: C
authors.lastname: D'Alfonso
authors.forename: Massimo
authors.initials: M
authors.lastname: Bietti
authors.forename: Gino A
authors.initials: GA
authors.lastname: DiLabio
authors.forename: Osvaldo
authors.initials: O
authors.lastname: Lanzalunga
authors.forename: Michela
authors.initials: M
authors.lastname: Salamone