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

L’ afiliació dels autors Laura Gómez, Scott T. Kleespies i Lawrence Que Jr són incorrectes en aquest article. L’errata està publicada a ’Nature Communications’, vol. 6, Article number: 6405 doi: http://dx.doi.org/10.1038/ncomms7405

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

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

Macmillan

Manager: Ministerio de Ciencia e Innovación (Espanya)
Author: Codolà Duch, Zoel
Gómez Martín, Laura
Kleespies, Scott T.
Que, Lawrence
Costas Salgueiro, Miquel
Lloret Fillol, Julio
Date: 2015
Abstract: L’ afiliació dels autors Laura Gómez, Scott T. Kleespies i Lawrence Que Jr són incorrectes en aquest article. L’errata està publicada a ’Nature Communications’, vol. 6, Article number: 6405 doi: http://dx.doi.org/10.1038/ncomms7405
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
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
Format: application/pdf
Document access: http://hdl.handle.net/10256/12258
Language: eng
Publisher: Macmillan
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1038/ncomms6865
info:eu-repo/semantics/altIdentifier/issn/2041-1723
MICINN/PN 2011/INP-2011-0059-PCT-420000
MICINN/PN 2010-2012/ CTQ2009-08464
info:eu-repo/grantAgreement/EC/FP7/239910/EU/Bio-inspired Design of Catalysts for Selective Oxidations of C-H and C=C Bonds/BIDECASEOX
info:eu-repo/grantAgreement/EC/FP7/268445/EU/Modular Ligands for Water Splitting/WATERSPLIT
Rights: Tots els drets reservats
Subject: Oxidació
Oxidation
Aigua -- Oxidació
Water -- Oxidation
Catalitzadors de ferro
Iron catalysts
Catàlisi
Catalysis
Title: Evidence for an ​oxygen evolving iron–oxo–cerium intermediate in iron-catalysed ​water oxidation
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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