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

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

doi:10.1039/c8sc00987b

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

Chem Sci. 2018 Jul 2;9(30):6379-6389. doi: 10.1039/c8sc00987b. eCollection 2018 Aug 14.

Authors

F Li¹, R L Meyer¹, S H Carpenter¹, L E VanGelder¹, A W Nichols², C W Machan², M L Neidig¹, E M Matson¹

Affiliations

¹ Department of Chemistry , University of Rochester , Rochester , New York 14627 , USA . Email: matson@chem.rochester.edu.
² Department of Chemistry , University of Virginia , Charlottesville , Virginia 22904-4319 , USA.

Abstract

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 ¹H 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.