Stoichiometric formation of an oxoiron(IV) complex by a soluble methane monooxygenase type activation of O2 at an iron(II)-cyclam centre
In soluble methane monooxygenase enzymes (sMMO) dioxy-gen (O2) is activated at a diiron(II) center to form an ox-odiiron(IV) intermediate Q that performs the challenging oxidation of methane to methanol. An analogous mechanism of O2 activation at mono- or di-nuclear iron centres is rare in the synth...
| Autores: | , , , , , , , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2020 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:10256/22839 |
| Acceso en línea: | http://hdl.handle.net/10256/22839 |
| Access Level: | acceso abierto |
| Palabra clave: | Hidrocarburs Cetones Lligands Oxidació Hydrocarbons Ketones Ligands Oxidation |
| Sumario: | In soluble methane monooxygenase enzymes (sMMO) dioxy-gen (O2) is activated at a diiron(II) center to form an ox-odiiron(IV) intermediate Q that performs the challenging oxidation of methane to methanol. An analogous mechanism of O2 activation at mono- or di-nuclear iron centres 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 inter-mediate 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 aro-matic C-H bonds of 2,6-di-tert-butylphenol, which, together with the strong OAT ability of 3 represent new domains of oxoiron(IV) and superoxoiron(III) reactivities |
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