The activation of dioxygen by nonheme iron centers is of fundamental importance to biological and synthetic oxidation reactivity. Dioxygen activation by nonheme iron is often proposed to follow a sequence of steps involving initial O2 binding, reduction of O2 to form a peroxo species, and O–O bond cleavage to produce a reactive high-valent FeIV(O) intermediate. Individual intermediates involved in these steps have been observed in both synthetic and enzymatic systems; however, the observation of multiple, sequentially formed Fe/oxygen intermediates is extremely rare. This presentation will discuss the reactivity of a dithiolate-ligated nonheme iron complex, FeII(Me3TACN)(S2SiMe2), with dioxygen to produce a peroxo(diiron) species, FeIII2(O2)(Me3TACN)2(S2SiMe2)2, which was characterized by UV-vis, Mössbauer, resonance Raman (RR), and X-ray absorption spectroscopies. This peroxo(diiron) complex undergoes photochemically or thermally induced O–O bond cleavage to generate an FeIV(O) complex, FeIV(O)(Me3TACN)(S2SiMe2), exhibiting a highly activated FeIV=O bond, as seen by RR and X-ray absorption spectroscopy. The FeIV(O) reacts with H-atom donors to produce an FeIII(OH) complex, FeIII(OH)(Me3TACN)(S2SiMe2), which could also be synthesized independently by addition of a one-electron oxidant followed by a hydroxide source to the FeII complex. The generation, stability, and spectroscopic characterization of each of these species will be discussed.

Activation of dioxygen by a mononuclear nonheme iron complex via sequential peroxo, oxo, and hydroxo intermediates

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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