We found a match
Your institution may have rights to this item. Sign in to continue.
- Title
An N-bridged high-valent diiron-oxo species on a porphyrin platform that can oxidize methane.
- Authors
Kudrik, Evgeny V.; Afanasiev, Pavel; Alvarez, Leonardo X.; Dubourdeaux, Patrick; Clémancey, Martin; Latour, Jean-Marc; Blondin, Geneviève; Bouchu, Denis; Albrieux, Florian; Nefedov, Sergey E.; Sorokin, Alexander B.
- 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.
- Subjects
PORPHYRINS; METHANE; ELECTRON paramagnetic resonance; ELECTROSPRAY ionization mass spectrometry; OXYGEN atom transfer reactions
- Publication
Nature Chemistry, 2012, Vol 4, Issue 12, p1024
- ISSN
1755-4330
- Publication type
Article
- DOI
10.1038/nchem.1471