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

Zoel Codolà; Laura Gómez; Scott T. Kleespies; Lawrence Que; Miquel Costas; Julio Lloret-Fillol

doi:10.1038/ncomms6865

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

Zoel Codolà, Laura Gómez, Scott T. Kleespies, Lawrence Que, Miquel Costas, Julio Lloret-Fillol

Chemistry (Twin Cities)

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Abstract

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.

Original language	English (US)
Article number	5865
Journal	Nature communications
Volume	6
DOIs	https://doi.org/10.1038/ncomms6865
State	Published - Jan 22 2015

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title = "Evidence for an oxygen evolving iron-oxo-cerium intermediate in iron-catalysed water oxidation",

abstract = "The non-haem iron complex α-[FeII(CF3SO3)2(mcp)] (mcp=(N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)-1,2-cis-diaminocyclohexane) reacts with CeIV 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)FeIV (O)(μ-O)CeIV(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 FeIV-O-CeIV adduct may open new pathways to validate mechanistic notions of an analogous MnV-O-CaII unit in the oxygen evolving complex that is responsible for carrying out the key O-O bond forming step.",

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AU - Codolà, Zoel

AU - Gómez, Laura

AU - Kleespies, Scott T.

AU - Que, Lawrence

AU - Costas, Miquel

AU - Lloret-Fillol, Julio

PY - 2015/1/22

Y1 - 2015/1/22

N2 - The non-haem iron complex α-[FeII(CF3SO3)2(mcp)] (mcp=(N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)-1,2-cis-diaminocyclohexane) reacts with CeIV 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)FeIV (O)(μ-O)CeIV(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 FeIV-O-CeIV adduct may open new pathways to validate mechanistic notions of an analogous MnV-O-CaII unit in the oxygen evolving complex that is responsible for carrying out the key O-O bond forming step.

AB - The non-haem iron complex α-[FeII(CF3SO3)2(mcp)] (mcp=(N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)-1,2-cis-diaminocyclohexane) reacts with CeIV 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)FeIV (O)(μ-O)CeIV(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 FeIV-O-CeIV adduct may open new pathways to validate mechanistic notions of an analogous MnV-O-CaII unit in the oxygen evolving complex that is responsible for carrying out the key O-O bond forming step.

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

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