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

Angew Chem Int Ed Engl. 2022 Jul 25;61(30):e202204570. doi: 10.1002/anie.202204570. Epub 2022 Jun 2.

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.

Keywords: Iron Nitrosyl; Perthionitrite; Reactive Sulfur Species; Thionitrite.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Iron* / chemistry
  • Nitrites
  • Nitroso Compounds*
  • Sulfhydryl Compounds
  • Sulfur

Substances

  • Nitrites
  • Nitroso Compounds
  • Sulfhydryl Compounds
  • perthionitrite
  • Sulfur
  • Iron