Selective Formation of an Fe^IV O or an Fe^III OOH Intermediate From Iron(II) and H₂ O₂ : Controlled Heterolytic versus Homolytic Oxygen-Oxygen Bond Cleavage by the Second Coordination Sphere

We demonstrate that the devised incorporation of an alkylamine group into the second coordination sphere of an Fe^II complex allows to switch its reactivity with H₂ O₂ from the usual formation of Fe^III species towards the selective generation of an Fe^IV -oxo intermediate. The Fe^IV -oxo species was characterized by UV/Vis absorption and Mössbauer spectroscopy. Variable-temperature kinetic analyses point towards a mechanism in which the heterolytic cleavage of the O-O bond is triggered by a proton transfer from the proximal to the distal oxygen atom in the Fe^II -H₂ O₂ complex with the assistance of the pendant amine. DFT studies reveal that this heterolytic cleavage is actually initiated by an homolytic O-O cleavage immediately followed by a proton-coupled electron transfer (PCET) that leads to the formation of the Fe^IV -oxo and release of water through a concerted mechanism.