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Stoichiometric Formation of an Oxoiron(IV) Complex by a Soluble Methane Monooxygenase Type Activation of O2 at an Iron(II)-Cyclam Center
Citation key Kass2020
Author Kass, Dustin and Corona, Teresa and Warm, Katrin and Braun-Cula, Beatrice and Kuhlmann, Uwe and Bill, Eckhard and Mebs, Stefan and Swart, Marcel and Dau, Holger and Haumann, Michael and Hildebrandt, Peter and Ray, Kallol
Pages 5924-5928
Year 2020
DOI 10.1021/jacs.9b13756
Journal Journal of the American Chemical Society
Volume 142
Number 13
Note PMID: 32168447
Abstract In soluble methane monooxygenase enzymes (sMMO), dioxygen (O2) 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 O2 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 O2 to form the corresponding iron(IV)-oxo complex, 2-trans, via a mechanism reminiscent of the O2 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 °C. Surprisingly, 3 is a stronger oxygen atom transfer (OAT) agent than 2-trans; 3 performs OAT to 1-trans or PPh3 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.
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