NO-to-[N2O2]2--to-N2O Conversion Triggered by {Fe(NO)2}10-{Fe(NO)2}9 Dinuclear Dinitrosyl Iron Complex.

Flavodiiron nitric oxide reductases (FNORs) evolved in some pathogens are known to detoxify NO via two-electron reduction to N2O to mitigate nitrosative stress. In this study, we describe how the electronically localized {Fe(NO)2}10-{Fe(NO)2}9 dinuclear dinitrosyl iron complex (dinuclear DNIC) [(NO)2Fe(μ-bdmap)Fe(NO)2(THF)] (2) (bdmap = 1,3-bis(dimethylamino)-2-propanolate) can induce a reductive coupling of NO to form hyponitrite-coordinated tetranuclear DNIC, which then converts to N2O. Upon the addition of 1 equiv of NO into the dinuclear {Fe(NO)2}10-{Fe(NO)2}9 DNIC 2, the proposed side-on-bound [NO]--bridged [(NO)2Fe(μ-bdmap)(κ2-NO) Fe(NO)2] intermediate may facilitate intermolecular (O)N-N(O) bond coupling to yield the paramagnetic tetranuclear quadridentate trans-hyponitrite-bound {[(NO)2Fe(μ-bdmap)Fe(NO)2]2(κ4-N2O2)} that transforms to [Fe(NO)2(μ-bdmap)]2, along with the release of N2O upon Hbdmap (1,3-bis(dimethylamino)-2-propanol) added.