Thionitrite (SNO <sup>−</sup> ) and Perthionitrite (SSNO <sup>−</sup> ) are Simple Synthons for Nitrosylated Iron Sulfur Clusters
Tobias J. Sherbow, Wen Fu, Lizhi Tao, Lev N. Zakharov, R. David Britt, Michael D. Pluth
Abstract
Abstract S/N crosstalk species derived from the interconnected reactivity of H 2 S and NO facilitate the transport of reactive sulfur and nitrogen species in signaling, transport, and regulatory processes. We report here that simple Fe 2+ 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 (S 5 )] − . In the reaction of FeCl 2 with SNO − we were able to isolate the unstable intermediate hydrosulfido mononitrosyl iron complex [FeCl 2 (NO)(SH)] − , which was characterized by X‐ray crystallography. We also show that [Fe(NO) 2 (S 5 )] − is a simple synthon for nitrosylated Fe−S clusters via its reduction with PPh 3 to yield Roussin's Red Salt ([Fe 2 S 2 (NO) 4 ] 2− ), which highlights the role of S/N crosstalk species in the assembly of fundamental Fe−S motifs.