Evidence for Low-Valent Electronic Configurations in Iron-Sulfur Clusters

Although biological iron-sulfur (Fe-S) clusters perform some of the most difficult redox reactions in nature, they are thought to be composed exclusively of Fe²⁺ and Fe³⁺ ions, as well as mixed-valent pairs with average oxidation states of Fe^2.5+. We herein show that Fe-S clusters formally composed of these valences can access a wider range of electronic configurations─in particular, those featuring low-valent Fe¹⁺ centers. We demonstrate that CO binding to a synthetic [Fe₄S₄]⁰ cluster supported by N-heterocyclic carbene ligands induces the generation of Fe¹⁺ centers via intracluster electron transfer, wherein a neighboring pair of Fe²⁺ sites reduces the CO-bound site to a low-valent Fe¹⁺ state. Similarly, CO binding to an [Fe₄S₄]⁺ cluster induces electron delocalization with a neighboring Fe site to form a mixed-valent Fe^1.5+Fe^2.5+ pair in which the CO-bound site adopts partial low-valent character. These low-valent configurations engender remarkable C-O bond activation without having to traverse highly negative and physiologically inaccessible [Fe₄S₄]⁰/[Fe₄S₄]^- redox couples.