Experiment and theory reveal the fundamental difference between two-state and single-state reactivity patterns in nonheme FeIV=O versus Ru IV=O oxidants

Abstract

(Chemical Equation Presented) Two-state reactivity involving close triplet ground and quintet excited states is responsible for the opposite reactivity trends of FeIV oxo complexes in O-transfer and H-abstraction reactions in dependence on the electron richness of the axial ligand X (see picture), as shown by comparison with RuIV analogues, in which both reactivities are solely governed by the electrophilicity of the complex because the quintet state is inaccessible. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.