Abstract
A zinc dithiolate complex supported by a [N3S2] ligand was studied as a model for zinc-mediated thiolate-disulfide exchange, enabling isolation of a zinc-bound mixed-disulfide intermediate. Solution-phase characterization of this zinc-disulfide complex indicates an interaction between the zinc center and the disulfide moiety that results in activation of the S-S bond for subsequent reactions. Comparison of this reaction with disulfide exchange by a previously prepared zinc tetrasulfanido complex demonstrates that sulfane sulfur (S0) acts as an efficient thiolate trapping agent, that is, polysulfanide anions are much less basic than thiolates. The resulting polysulfanide anions also exhibit decreased nucleophilicity compared to the parent thiolate anions. Alkylation kinetics comparisons between the zinc dithiolate and zinc tetrasulfanido complexes indicate attenuation of zinc-bound thiolate nucleophilicity by sulfane. These results suggest a general interplay between zinc, sulfane, and thiol/thiolate reactivity that can significantly impact biological redox processes.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
