Reactivity of an All-Ferrous Iron–Nitrogen Heterocubane under Reductive and Oxidative Conditions

The reactivity of the all-ferrous FeN heterocubane [Fe₄(Ntrop)₄] (1) with i) Brønsted acids, ii) σ-donors, iii) σ-donors/π-acceptors, and iv) one-electron oxidants has been investigated (trop = 5H-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(μ₃-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.