Revisiting the Hammett ρ Parameter for the Determination of Philicity: Nucleophilic Substitution with Inverse Charge Interaction

Recent work identified a fascinating charge/FMO control dichotomy in oxidations of substituted phenyl sulfoxides. A great read for those interested in FMO theory, the role of partial charges in controlling reaction pathways, and/or linear free energy relationships.

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).

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