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

Nature Chemistry volume 4, pages 1024–1029 (2012)Cite this article

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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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Figure 1: Low-temperature UV-vis spectroscopic study of the reaction of 1 with m-CPBA.
Figure 2: Mössbauer spectra of a 57Fe-enriched sample of 3.
Figure 3

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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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Authors and Affiliations

  1. 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, Villeurbanne Cedex, 69626, France

    Evgeny V. Kudrik, Pavel Afanasiev, Leonardo X. Alvarez & Alexander B. Sorokin

  2. Commissariat à l'Energie Atomique et aux Energies Alternatives, l'Institut de Recherches en Technologies et Sciences pour le Vivant/Laboratoire de Chimie et Biologie des Métaux, 17 rue des Martyrs, Grenoble, 38054, France

    Patrick Dubourdeaux, Martin Clémancey, Jean-Marc Latour & Geneviève Blondin

  3. Centre National de la Recherche Scientifique, Unité Mixte de Recherche 5249, Grenoble, 38054, France

    Patrick Dubourdeaux, Martin Clémancey, Jean-Marc Latour & Geneviève Blondin

  4. Université Joseph Fourier, Grenoble, 38054, France

    Patrick Dubourdeaux, Martin Clémancey, Jean-Marc Latour & Geneviève Blondin

  5. Université Lyon 1, Unité Mixte de Recherche 5246, Centre Commun de Spectrométrie de Masse, 43 Boulevard du 11 Novembre 1918, Villeurbanne Cedex, 69622, France

    Denis Bouchu & Florian Albrieux

  6. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Science, 31 Leninskii Avenue, Moscow, 119991, Russia

    Sergey E. Nefedov

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  1. Evgeny V. Kudrik
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Contributions

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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Correspondence to Geneviève Blondin or Alexander B. Sorokin.

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Supplementary information

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Crystallographic data for compound 1. (CIF 21 kb)

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Crystallographic data for compound 1a. (CIF 27 kb)

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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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