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)

Research output: Contribution to journal › Article › peer-review

78 Scopus citations

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

Bibliographical note

Funding Information:
We thank Dr. Xavi Ribas and Dr. Anna Company for reading this work and for helpful comments. We also thank the European Research Foundation for project FP7-PEOPLE-2010-ERG-268445 (J.L.-F), MICINN for project CTQ2009-08464 (M.C.) and for a Ramon y Cajal contract (J.L.-F.), Generalitat de Catalunya for an ICREA Academia Award and the European Research Foundation for Project ERC-2009-StG-239910 (M.C.). The work carried out at the University of Minnesota was supported by US National Institutes of Health grant GM38767 to L.Q. We appreciate financial support from INNPLANTA project INP-2011-0059-PCT-420000-ACT1 to Dr. X. Ribas.

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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.",

author = "Zoel Codol{\`a} and Laura G{\'o}mez and Kleespies, {Scott T.} and Lawrence Que and Miquel Costas and Julio Lloret-Fillol",

note = "Funding Information: We thank Dr. Xavi Ribas and Dr. Anna Company for reading this work and for helpful comments. We also thank the European Research Foundation for project FP7-PEOPLE-2010-ERG-268445 (J.L.-F), MICINN for project CTQ2009-08464 (M.C.) and for a Ramon y Cajal contract (J.L.-F.), Generalitat de Catalunya for an ICREA Academia Award and the European Research Foundation for Project ERC-2009-StG-239910 (M.C.). The work carried out at the University of Minnesota was supported by US National Institutes of Health grant GM38767 to L.Q. We appreciate financial support from INNPLANTA project INP-2011-0059-PCT-420000-ACT1 to Dr. X. Ribas.",

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AU - Codolà, Zoel

AU - Gómez, Laura

AU - Kleespies, Scott T.

AU - Que, Lawrence

AU - Costas, Miquel

AU - Lloret-Fillol, Julio

N1 - Funding Information: We thank Dr. Xavi Ribas and Dr. Anna Company for reading this work and for helpful comments. We also thank the European Research Foundation for project FP7-PEOPLE-2010-ERG-268445 (J.L.-F), MICINN for project CTQ2009-08464 (M.C.) and for a Ramon y Cajal contract (J.L.-F.), Generalitat de Catalunya for an ICREA Academia Award and the European Research Foundation for Project ERC-2009-StG-239910 (M.C.). The work carried out at the University of Minnesota was supported by US National Institutes of Health grant GM38767 to L.Q. We appreciate financial support from INNPLANTA project INP-2011-0059-PCT-420000-ACT1 to Dr. X. Ribas.

PY - 2015/1/22

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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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