| Zitatschlüssel |
Kass2020 |
| Autor |
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 |
| Seiten |
5924-5928 |
| Jahr |
2020 |
| DOI |
10.1021/jacs.9b13756 |
| Journal |
Journal of the American Chemical Society |
| Jahrgang |
142 |
| Nummer |
13 |
| Notiz |
PMID: 32168447 |
| Zusammenfassung |
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. |
