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• W2902046052 abstract "Abstract 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 H 2 O 2 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 ‐H 2 O 2 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." @default.
• W2902046052 created "2018-12-11" @default.
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• W2902046052 date "2018-12-17" @default.
• W2902046052 modified "2023-10-18" @default.
• W2902046052 title "Selective Formation of an Fe^IVO or an Fe^IIIOOH Intermediate From Iron(II) and H₂O₂: Controlled Heterolytic versus Homolytic Oxygen–Oxygen Bond Cleavage by the Second Coordination Sphere" @default.
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• W2902046052 doi "https://doi.org/10.1002/anie.201812724" @default.
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