Thionitrite (SNO ⁻ ) and Perthionitrite (SSNO ⁻ ) are Simple Synthons for Nitrosylated Iron Sulfur Clusters

Abstract

S/N crosstalk species derived from the interconnected reactivity of H₂ S and NO facilitate the transport of reactive sulfur and nitrogen species in signaling, transport, and regulatory processes. We report here that simple Fe²⁺ ions, such as those that are bioavailable in the labile iron pool (LIP), react with thionitrite (SNO^- ) and perthionitrite (SSNO^- ) to yield the dinitrosyl iron complex [Fe(NO)₂ (S₅ )]^- . In the reaction of FeCl₂ with SNO^- we were able to isolate the unstable intermediate hydrosulfido mononitrosyl iron complex [FeCl₂ (NO)(SH)]^- , which was characterized by X-ray crystallography. We also show that [Fe(NO)₂ (S₅ )]^- is a simple synthon for nitrosylated Fe-S clusters via its reduction with PPh₃ to yield Roussin's Red Salt ([Fe₂ S₂ (NO)₄ ]^2- ), which highlights the role of S/N crosstalk species in the assembly of fundamental Fe-S motifs.