Sulfur is involved in a broad range of biological processes, but its storage, modification, and transport are not well understood, particularly at transition-metal-containing sites. Here, we show that a biomimetic zinc dithiolate complex inserts elemental sulfur into the zinc-thiolate bond to form an unusual zinc tetrasulfanido complex. Chemical oxidation of the zinc tetrasulfanido complex results in rearrangement to form bimetallic complexes and extrusion of elemental sulfur. Reduction results in the generation of sulfur anions and recovery of the parent zinc dithiolate complex. The zinc tetrasulfanido complex transfers sulfur atoms to electrophiles such as electron poor alkynes and organodisulfides. The reaction of the zinc tetrasulfanido complex with alkyl disulfides generates a charge-transfer adduct which catalyzes sulfur atom transfer from elemental sulfur to alkyl disulfides to generate higher order alkyl polysulfides. These results have broader implications for the role that transition metal polysulfanido complexes may have under biological conditions.

Sulfur-centered reactions of a zinc tetrasulfanido complex: Redox and sulfur atom transfer

ACS Spring Meeting 2021

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