Abstract
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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Acknowledgements
This work was supported by grant ANR-08-BLANC-0183-01 from Agence National de la Recherche (ANR, France). The Rhône-Alpes region is acknowledged for the financial support SRESR-CIBLE 2008 and CIBLE 07 016335. We thank B. Albela and L. Bonneviot for the help with EPR measurements.
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E.V.K., P.A., J.M.L., G.B. and A.B.S. conceived and designed the experiments. E.V.K., P.A., L.X.A., P.D., M.C., D.B., F.A. and S.E.N. performed the experiments. P.A., M.C., J.M.L., G.B. and A.B.S. analysed the data. J.M.L., G.B. and A.B.S. co-wrote the manuscript.
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Kudrik, E., Afanasiev, P., Alvarez, L. et al. An N-bridged high-valent diiron–oxo species on a porphyrin platform that can oxidize methane. Nature Chem 4, 1024–1029 (2012). https://doi.org/10.1038/nchem.1471
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DOI: https://doi.org/10.1038/nchem.1471
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