Understanding Hydrogen Sulfide Storage: Probing Conditions for Sulfide Release from Hydrodisulfides

[Image: see text] Hydrogen sulfide (H(2)S) is an important biological signaling agent that exerts action on numerous (patho)physiological processes. Once generated, H(2)S can be oxidized to generate reductant-labile sulfane sulfur pools, which include hydrodisulfides/persulfides. Despite the importance of hydrodisulfides in H(2)S storage and signaling, little is known about the physical properties or chemical reactivity of these compounds. We report here the synthesis, isolation, and characterization (NMR, IR, Raman, HRMS, X-ray) of a small-molecule hydrodisulfide and highlight its reactivity with reductants, nucleophiles, electrophiles, acids, and bases. Our experimental results establish that hydrodisulfides release H(2)S upon reduction and that deprotonation results in disproportionation to the parent thiol and S(0), thus providing a mechanism for transsulfuration in the sulfane sulfur pool.