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

作者：Li F; Meyer R L; Carpenter S H; VanGelder L E; Nichols A W; Machan C W; Neidig M L; Matson E M^*

来源：Chemical Science, 2018, 9(30): 6379-6389.

DOI：10.1039/c8sc00987b

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 [(V3V2IV)-V-V]{FeNO}(7) to [V-5(IV)]{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.

• 出版日期2018-8-14