Low-valent iron centers are critical intermediates in chemical and bio-chemical processes. Herein, we show the first example of a low-valent FeI center stabilized in a high-valent polyoxometalate framework. Electrochemical studies show that the FeIII-functionalized molecular vanadium(V) oxide (DMA)[FeIIIClVV O Cl]3? (DMA=dimethylammonium) features two well-defined, reversible, iron-based electrochemical reductions which cleanly yield the FeI species (DMA)[FeIClVV O Cl]5?.
