Nitric oxide activation facilitated by cooperative multimetallic electron transfer within an iron-functionalized polyoxovanadate–alkoxide cluster

A series of NO-bound, iron-functionalized polyoxovanadate–alkoxide (FePOV–alkoxide) clusters have been synthesized, providing insight into the role of multimetallic constructs in the coordination and activation of a substrate. Upon exposure of the heterometallic cluster to NO, the vanadium-oxide metalloligand is oxidized by a single electron, shuttling the reducing equivalent to the {FeNO} subunit to form a {FeNO}(7) species. Four NO-bound clusters with electronic distributions ranging from [VV3VIV2]{FeNO}(7) to [VIV5]{FeNO}(7) have been synthesized, and characterized via(1)H NMR, infrared, and electronic absorption spectroscopies. The ability of the FePOV–alkoxide cluster to store reducing equivalents in the metalloligand for substrate coordination and activation highlights the ultility of the metal-oxide scaffold as a redox reservoir.