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Reactivity of an All‐Ferrous Iron–Nitrogen Heterocubane under Reductive and Oxidative Conditions
Author(s) -
Lichtenberg Crispin,
Prokopchuk Demyan E.,
Adelhardt Mario,
Viciu Liliana,
Meyer Karsten,
Grützmacher Hansjörg
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201502530
Subject(s) - ferrous , reactivity (psychology) , oxidative phosphorylation , chemistry , nitrogen , biochemistry , medicine , organic chemistry , pathology , alternative medicine
The reactivity of the all‐ferrous FeN heterocubane [Fe 4 (Ntrop) 4 ] ( 1 ) with i) Brønsted acids, ii) σ‐donors, iii) σ‐donors/π‐acceptors, and iv) one‐electron oxidants has been investigated (trop = 5 H ‐dibenzo[ a , d ]cyclo‐hepten‐5‐yl). 1 showed self‐re‐assembling after reactions with i) and proved surprisingly inert in reactions with ii) and iii), with the exception of CO. Reductive and oxidative cluster degradation was observed in reactions with CO and TEMPO, respectively. These reactions yielded new cluster compounds, namely a trinuclear bis(μ 3 ‐imido) 48 electron complex in the former case and a tetranuclear all ferric μ‐oxo‐μ‐imido species in the latter case. Characterization techniques include NMR and in situ IR spectroscopy, single crystal X‐ray analysis, Mössbauer spectroscopy, cyclic voltammetry, magnetic susceptibility measurements, and DFT calculations.