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Nat Chem. 2012 Dec;4(12):1024-9. doi: 10.1038/nchem.1471. Epub 2012 Oct 14.

An N-bridged high-valent diiron-oxo species on a porphyrin platform that can oxidize methane.

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Institut de Recherches sur la Catalyse et l'Environnement de Lyon, Unité Mixte de Recherche 5256, Centre National de la Recherche Scientifique, Université Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex, France.


High-valent oxo-metal complexes are involved in key biochemical processes of selective oxidation and removal of xenobiotics. The catalytic properties of cytochrome P-450 and soluble methane monooxygenase enzymes are associated with oxo species on mononuclear iron haem and diiron non-haem platforms, respectively. Bio-inspired chemical systems that can reproduce the fascinating ability of these enzymes to oxidize the strongest C-H bonds are the focus of intense scrutiny. In this context, the development of highly oxidizing diiron macrocyclic catalysts requires a structural determination of the elusive active species and elucidation of the reaction mechanism. Here we report the preparation of an Fe(IV)(µ-nitrido)Fe(IV) = O tetraphenylporphyrin cation radical species at -90 °C, characterized by ultraviolet-visible, electron paramagnetic resonance and Mössbauer spectroscopies and by electrospray ionization mass spectrometry. This species exhibits a very high activity for oxygen-atom transfer towards alkanes, including methane. These findings provide a foundation on which to develop efficient and clean oxidation processes, in particular transformations of the strongest C-H bonds.

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