Soluble methane monooxygenase (sMMO) is an enzyme found in methanotrophic organisms that carry out the oxidation of methane to methanol at ambient temperature and pressure. The enzymatic cycle of sMMO involves the formation of a peroxodiiron(III) intermediate (P) that gives rise to a diiron(IV) complex (Q), which is the species responsible for methane hydroxylation. Synthetic models for Q are rare, and none of these are formed by mimicking the conversion of P to Q. In this work, [FeII(Me3NTB)(CH3CN)](CF3SO3)2 (Me3NTB = tris((1-methyl-1H-benzo[d]imidazol-2-yl)methyl)amine) is found to react with dioxygen to generate a peroxodiiron(III) intermediate, which has been characterized using a variety of spectroscopic methods. This complex undergoes acid-assisted O–O bond cleavage to generate a bis(μ-oxo)diiron(IV) complex, representing the first synthetic system to model the conversion of P to Q in the sMMO reaction cycle.

Modeling steps in the sMMO reaction cycle: Forming a diiron(IV) complex via acid-assisted O–O bond cleavage of a peroxodiiron(III) intermediate derived from O2

2019 Spring National Meeting

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