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

作者:Kudrik Evgeny V; Afanasiev Pavel; Alvarez Leonardo X; Dubourdeaux Patrick; Clemancey Martin; Latour Jean Marc; Blondin Genevieve*; Bouchu Denis; Albrieux Florian; Nefedov Sergey E; Sorokin Alexander B
来源:Nature Chemistry, 2012, 4(12): 1024-1029.
DOI:10.1038/NCHEM.1471

摘要

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)(mu-nitrido)Fe(IV) = O tetraphenylporphyrin cation radical species at -90 degrees C, characterized by ultraviolet-visible, electron paramagnetic resonance and Mossbauer 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.

  • 出版日期2012-12