Revisiting the Hammett ρ parameter for the determination of philicity: Nucleophilic substitution with inverse charge interaction

Abstract

Too OT to handle? In oxygen transfer (OT) reactions the inversion of the ρ value is not representative of a change in mechanism. Substituents bonded to aromatic sulfoxides have the opposite effect on the rates of oxidation depending on whether the reaction is dominated by electrostatic or orbital-overlap effects (see picture). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.