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Stabilization of Low‐Valent Iron(I) in a High‐Valent Vanadium(V) Oxide Cluster
Author(s) -
Anjass Montaha H.,
Kastner Katharina,
Nägele Florian,
Ringenberg Mark,
Boas John F.,
Zhang Jie,
Bond Alan M.,
Jacob Timo,
Streb Carsten
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201706828
Subject(s) - polyoxometalate , chemistry , vanadium , vanadium oxide , electrochemistry , electron paramagnetic resonance , catalysis , inorganic chemistry , oxide , density functional theory , cluster (spacecraft) , electron transfer , metal , transition metal , crystallography , photochemistry , computational chemistry , organic chemistry , nuclear magnetic resonance , physics , electrode , computer science , programming language
Low‐valent iron centers are critical intermediates in chemical and bio‐chemical processes. Herein, we show the first example of a low‐valent Fe I center stabilized in a high‐valent polyoxometalate framework. Electrochemical studies show that the Fe III ‐functionalized molecular vanadium(V) oxide (DMA)[Fe III ClV V 12 O 32 Cl] 3− (DMA=dimethylammonium) features two well‐defined, reversible, iron‐based electrochemical reductions which cleanly yield the Fe I species (DMA)[Fe I ClV V 12 O 32 Cl] 5− . Experimental and theoretical studies including electron paramagnetic resonance spectroscopy and density functional theory computations verify the formation of the Fe I species. The study presents the first example for the seemingly paradoxical embedding of low‐valent metal species in high‐valent metal oxide anions and opens new avenues for reductive electron transfer catalysis by polyoxometalates.