S/N crosstalk species derived from the interconnected reactivity of H S and NO facilitate the transport of reactive sulfur and nitrogen species in signaling, transport, and regulatory processes. We report here that simple Fe 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) (S )] . In the reaction of FeCl with SNO we were able to isolate the unstable intermediate hydrosulfido mononitrosyl iron complex [FeCl (NO)(SH)] , which was characterized by X-ray crystallography. We also show that [Fe(NO) (S )] is a simple synthon for nitrosylated Fe-S clusters via its reduction with PPh to yield Roussin's Red Salt ([Fe S (NO) ] ), which highlights the role of S/N crosstalk species in the assembly of fundamental Fe-S motifs.
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http://dx.doi.org/10.1002/anie.202204570 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Department of Chemistry and Biochemistry, Materials Science Institute, Knight Campus for Accelerating Scientific Impact, Institute of Molecular Biology, 1253 University of Oregon, Eugene, Oregon, 97403, United States.
Hydrogen sulfide (HS) and nitric oxide (NO) are important gaseous biological signaling molecules that are involved in complex cellular pathways. A number of physiological processes require both HS and NO, which has led to the proposal that different HS/NO⋅ crosstalk species, including thionitrite (SNO) and perthionitrite (SSNO), are responsible for this observed codependence. Despite the importance of these S/N hybrid species, the reported properties and characterization, as well as the fundamental pathways of formation and subsequent reactivity, remain poorly understood.
View Article and Find Full Text PDFInorg Chem
August 2024
School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, West Bengal, India.
A comparative bioinspired reactivity study of new binuclear Zn(II) complexes featuring coordinated thiolate, selenolate, trisulfide and diselenide in relation with (i) the generation of reactive sulfur/selenium species (RSS/RSeS), (ii) the oxygen dependent oxidation and disproportionation of polysulfide (S) to produce sulfite (SO), thiosulfate (SO) and sulfide (S) by sulfur oxygenase reductase (SOR), and (iii) the reaction of S with nitrite (NO) to generate thionitrite (SNO), perthionitrite (SSNO) and nitric oxide (NO), is presented. The binuclear Zn(II)-thiolate/selenolate complexes could react with elemental sulfur to generate RSS/RSeS while similar reactions involving elemental selenium could not generate RSeS. The dizinc(II)-S and the dizinc(II)-Se complexes could react with dioxygen (O) to generate binuclear Zn(II) complexes featuring coordinated thiosulfate (SO) and selenite (SeO), respectively.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2023
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram (IISER-Tvm) Thiruvananthapuram, 695551, Kerala, India.
(Per)thionitrite (SNO /SSNO ) intermediates play vital roles in modulating nitric oxide (NO) and hydrogen sulfide (H S) dependent bio-signalling processes. Whilst the previous preparations of such intermediates involved reactive H S/HS or sulfane sulfur (S ) species, the present report reveals that relatively stable thiocarbonyl compounds (such as carbon disulfide (CS ), thiocarbamate, thioacetic acid, and thioacetate) react with nitrite anion to yield SNO /SSNO . For instance, the reaction of CS and nitrite anion (NO ) under ambient condition affords CO and SNO /SSNO .
View Article and Find Full Text PDFMolecules
May 2023
Core Unit Proteomics, Institute of Toxicology, Hannover Medical School, 30625 Hannover, Germany.
Nitrite (O=N-O, NO) and nitrate (O=N(O)-O, NO) are ubiquitous in nature. In aerated aqueous solutions, nitrite is considered the major autoxidation product of nitric oxide (NO). NO is an environmental gas but is also endogenously produced from the amino acid L-arginine by the catalytic action of NO synthases.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2022
Department of Chemistry and Biochemistry, Materials Science Institute, Knight Campus for Accelerating Scientific Impact, and Institute of Molecular Biology, University of Oregon, Eugene, OR 97403-1253, USA.
S/N crosstalk species derived from the interconnected reactivity of H S and NO facilitate the transport of reactive sulfur and nitrogen species in signaling, transport, and regulatory processes. We report here that simple Fe 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) (S )] . In the reaction of FeCl with SNO we were able to isolate the unstable intermediate hydrosulfido mononitrosyl iron complex [FeCl (NO)(SH)] , which was characterized by X-ray crystallography.
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