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Water Oxidation Reaction Mediated by an Octanuclear Iron‐Oxo Cluster
Author(s) -
Deutscher Jennifer,
Corona Teresa,
Warm Katrin,
Engelmann Xenia,
Sobottka Sebastian,
BraunCula Beatrice,
Sarkar Biprajit,
Ray Kallol
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201800269
Subject(s) - chemistry , ferrihydrite , maghemite , magnetite , hydrogen peroxide , electrochemistry , polyoxometalate , cluster (spacecraft) , inorganic chemistry , hematite , crystallography , catalysis , adsorption , organic chemistry , mineralogy , materials science , electrode , computer science , metallurgy , programming language
A one‐pot synthetic procedure yields the octanuclear Fe III complex [Fe 8 (µ 4 ‐O) 4 (µ ‐ 4‐ t Bu‐pz) 12 Cl 4 ] ( 2 ). The molecular structure of 2 resembles the building units of iron‐containing minerals like magnetite, ferrihydrite and maghemite. Based on mechanistic investigation we propose that in presence of Et 3 N, iron(III) pyrazolates are reduced to iron(II) pyrazolates, which then activate dioxygen to form 2 . Complex 2 exhibits unique spectroscopic and electrochemical properties relative to those of the previously reported Fe 8 clusters based on pyrazolate ligands. Furthermore, 2 can oxidize water to hydrogen peroxide, thereby mimicking the water splitting process taking place at the surface of magnetite. Compound 2 therefore acts as both structural and functional models of iron‐containing minerals.