High-valent iron-oxo species are generated by metalloenzyme-catalyzed dioxygen activation, examples of which include the mononuclear oxoiron(IV) oxidants associated with TauD and related halogenases and the FeIV2O2 diamond core found for intermediate Q of soluble methane monooxygenase (sMMO). In both types, the high-valent iron center has an S = 2 ground spin state. Our recent efforts have led to the design of ligands that support high-valent iron centers and shed light on how these intermediates may function. S = 2 FeIV=O species have been generated that exhibit high rates of cyclohexane oxidation comparable to those associated with enzymatic FeIV=O intermediates. Extension of this effort to modeling the corresponding nonheme iron halogenases has resulted in the generation and spectroscopic characterization of [FeIV(O)(L)(Cl/Br)] complexes that halogenate hydrocarbons. Synthetic complexes have also provided insight into the assembly of the FeIV2O2 diamond core of sMMO-Q and how it may react with hydrocarbon substrates.

Award Address (ACS Award in Inorganic Chemistry sponsored by Aldrich Chemical Company, LLC). Amazing nonheme high-valent iron-oxo landscape

253rd National Meeting (2017)

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