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Journal Article

Stoichiometric Formation of an Oxoiron(IV) Complex by a Soluble Methane Monooxygenase Type Activation of O-2 at an Iron(II)-Cyclam Center

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Bill,  Eckhard
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Hildebrandt,  Peter
Department of Spectroscopy and Photochemical Kinetics, MPI for biophysical chemistry, Max Planck Society;
Abteilung Spektroskopie, MPI for biophysical chemistry, Max Planck Society;

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Citation

Kass, D., Corona, T., Warm, K., Braun-Cula, B., Kuhlmann, U., Bill, E., et al. (2020). Stoichiometric Formation of an Oxoiron(IV) Complex by a Soluble Methane Monooxygenase Type Activation of O-2 at an Iron(II)-Cyclam Center. Journal of the American Chemical Society, 142(13), 5924-5928. doi:10.1021/jacs.9b13756.


Cite as: https://hdl.handle.net/21.11116/0000-0007-B3B7-0
Abstract
In soluble methane monooxygenase enzymes (sMMO), dioxygen (O-2) is activated at a diiron(II) center to form an oxodiiron(IV) intermediate Q that performs the challenging oxidation of methane to methanol. An analogous mechanism of O-2 activation at mono- or dinuclear iron centers is rare in the synthetic chemistry. Herein, we report a mononuclear non-heme iron(II)cyclam complex, 1-trans, that activates O-2 to form the corresponding iron(IV)-oxo complex, 2-trans, via a mechanism reminiscent of the O-2 activation process in sMMO. The conversion of 1-trans to 2-trans proceeds via the intermediate formation of an iron(III)-superoxide species 3, which could be trapped and spectroscopically characterized at -50 degrees C. Surprisingly, 3 is a stronger oxygen atom transfer (OAT) agent than 2-trans; 3 performs OAT to 1-trans or PPh 3 to yield 2-trans quantitatively. Furthermore, 2-trans oxidizes the aromatic C-H bonds of 2,6-di-tert-butylphenol, which, together with the strong OAT ability of 3, represents new domains of oxoiron(IV) and superoxoiron(III) reactivities.