A Monohydrosulfidodinitrosyldiiron Complex That Generates N₂O as a Model for Flavodiiron Nitric Oxide Reductases:...

Flavodiiron nitric oxide reductases (FNORs) protect microbes from nitrosative stress under anaerobic conditions by mediating the reduction of nitric oxide (NO) to nitrous oxide (N₂O). The proposed mechanism for the catalytic reduction of NO by FNORs involves a dinitrosyldiiron intermediate with a [hs-{FeNO}⁷]₂ formulation, which produces N₂O and a diferric species. Moreover, both NO and hydrogen sulfide (H₂S) have been implicated in several similar physiological functions in biology and are also known to cross paths in cell signaling. Here we report the synthesis, spectroscopic and theoretical characterization, and N₂O production activity of an unprecedented monohydrosulfidodinitrosyldiiron compound, with a [(HS)hs-{FeNO}⁷/hs-{FeNO}⁷] formulation, that models the key dinitrosyl intermediate of FNORs. The generation of N₂O from this unique compound follows a semireduced pathway, where one-electron reduction generates a reactive hs-{FeNO}⁸ center via the occupation of an Fe-NO antibonding orbital. In contrast to the well-known reactivity of H₂S and NO, the coordinated hydrosulfide remains unreactive toward NO and acts only as a spectator ligand during the NO reduction process.