Generation of Thiosulfate, Selenite, Dithiosulfite, Perthionitrite, Nitric Oxide, and Reactive Chalcogen Species by Binuclear Zinc(II)-Chalcogenolato/-Polychalcogenido Complexes.

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. Finally, unlike the nonreactive nature of the dizinc(II)-Se complex toward NO, reaction of the dizinc(II)-S complex with NO produced a new binuclear Zn(II) complex featuring a coordinated dithiosulfite (SO) along with the formation of perthionitrite (SSNO), of which the latter subsequently produced nitric oxide (NO) and S. The present work, thus, demonstrates the comparative reactivity of a series of binuclear Zn(II)-chalcogenolato/-polychalcogenido complexes for the generation of SO, SeO, SO, SSNO, NO and RSS/RSeS.