Evidence for an oxygen evolving iron-oxo-cerium intermediate in iron-catalysed water oxidation

The non-haem iron complex α-[Fe(II)(CF3SO3)2(mcp)] (mcp=(N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-1,2-cis-diaminocyclohexane) reacts with Ce(IV) to oxidize water to O2, representing an iron-based functional model for the oxygen evolving complex of photosystem II. Here we trap an intermediat...

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Bibliographic Details
Published in:Nature communications 2015-01, Vol.6 (1), p.5865-5865, Article 5865
Main Authors: Codolà, Zoel, Gómez, Laura, Kleespies, Scott T, Que, Jr, Lawrence, Costas, Miquel, Lloret-Fillol, Julio
Format: Article
Language:English
Subjects:
Aqueous solutions
Bacteria - metabolism
Catalysis
Cerium - chemistry
Hydrogen-Ion Concentration
Iron - chemistry
Kinetics
Ligands
Mass spectrometry
Mass Spectrometry - methods
Oxidation
Oxygen - chemistry
Photosystem II Protein Complex - chemistry
Scientific imaging
Spectrometry, Mass, Electrospray Ionization
Spectrophotometry, Ultraviolet
Spectrum Analysis, Raman - methods
Water - chemistry
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Summary:The non-haem iron complex α-[Fe(II)(CF3SO3)2(mcp)] (mcp=(N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-1,2-cis-diaminocyclohexane) reacts with Ce(IV) to oxidize water to O2, representing an iron-based functional model for the oxygen evolving complex of photosystem II. Here we trap an intermediate, characterized by cryospray ionization high resolution mass spectrometry and resonance Raman spectroscopy, and formulated as [(mcp)Fe(IV)(O)(μ-O)Ce(IV)(NO3)3](+), the first example of a well-characterized inner-sphere complex to be formed in cerium(IV)-mediated water oxidation. The identification of this reactive Fe(IV)-O-Ce(IV) adduct may open new pathways to validate mechanistic notions of an analogous Mn(V)-O-Ca(II) unit in the oxygen evolving complex that is responsible for carrying out the key O-O bond forming step.
ISSN:2041-1723
2041-1723
DOI:10.1038/ncomms6865