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

被引：120
作者：
Codola, Zoel [1 ,2 ]
Gomez, Laura [3 ,4 ]
Kleespies, Scott T. [5 ]
Que, Lawrence, Jr. [5 ]
Costas, Miquel [1 ,2 ]
Lloret-Fillol, Julio [1 ,2 ]
机构：
[1] Univ Girona, Inst Quim Computac & Catalisi, Girona 17071, Spain
[2] Univ Girona, Dept Quim, Girona 17071, Spain
[3] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA
[4] Univ Minnesota, Ctr Met Biocatalysis, Minneapolis, MN 55455 USA
[5] Univ Girona, Serv Tecnics Recerca, Girona 17003, Spain
来源：
NATURE COMMUNICATIONS | 2015年 / 6卷
基金：
美国国家卫生研究院;
关键词：
O BOND FORMATION; PHOTOSYSTEM-II; METHANE MONOOXYGENASE; CIS-DIHYDROXYLATION; SYNTHETIC MODEL; COMPLEXES; LIGAND; MECHANISM; CORES; PEROXODIIRON(III);
D O I：
10.1038/ncomms6865
中图分类号：
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号：
07 ; 0710 ; 09 ;
摘要：
The non-haem iron complex alpha-[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 O-2, 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) (mu-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.
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页数：9
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