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A Low‐Valent Iron Imido Heterocubane Cluster: Reversible Electron Transfer and Catalysis of Selective C–C Couplings
Author(s) -
Lichtenberg Crispin,
Garcia Rubio Inés,
Viciu Liliana,
Adelhardt Mario,
Meyer Karsten,
Jeschke Gunnar,
Grützmacher Hansjörg
Publication year - 2015
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.201505668
Subject(s) - electron transfer , catalysis , chemistry , redox , unpaired electron , electron , reagent , cluster (spacecraft) , selectivity , sulfur , oxidation state , ground state , photochemistry , crystallography , inorganic chemistry , molecule , atomic physics , organic chemistry , physics , quantum mechanics , computer science , programming language
Enzymes and cofactors with iron–sulfur heterocubane core structures, [Fe 4 S 4 ], are often found in nature as electron transfer reagents in fundamental catalytic transformations. An artificial heterocubane with a [Fe 4 N 4 ] core is reported that can reversibly store up to four electrons at very negative potentials. The neutral [Fe 4 N 4 ] and the singly reduced low‐valent [Fe 4 N 4 ] − heterocubanes were isolated and fully characterized. The low‐valent species bears one unpaired electron, which is localized predominantly at one iron center in the electronic ground state but fluctuates with increasing temperatures. The electrons stored or released by the [Fe 4 N 4 ]/[Fe 4 N 4 ] − redox couple can be used in reductive or oxidative CC couplings and even allow catalytic one‐pot reactions, which show a remarkably enhanced selectivity in the presence of the [Fe 4 N 4 ] heterocubanes.