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 n 2- ) to produce sulfite (SO 3 2- ), thiosulfate (S 2 O 3 2- ) and sulfide (S 2- ) by sulfur oxygenase reductase (SOR), and (iii) the reaction of S n 2- with nitrite (NO 2 - ) 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 3 and the dizinc(II)-Se 2 complexes could react with dioxygen (O 2 ) to generate binuclear Zn(II) complexes featuring coordinated thiosulfate (S 2 O 3 2- ) and selenite (SeO 3 2- ), respectively. Finally, unlike the nonreactive nature of the dizinc(II)-Se 2 complex toward NO 2 - , reaction of the dizinc(II)-S 3 complex with NO 2 - produced a new binuclear Zn(II) complex featuring a coordinated dithiosulfite (S 3 O 2- ) along with the formation of perthionitrite (SSNO - ), of which the latter subsequently produced nitric oxide (NO) and S 4 2- . The present work, thus, demonstrates the comparative reactivity of a series of binuclear Zn(II)-chalcogenolato/-polychalcogenido complexes for the generation of S 2 O 3 2- , SeO 3 2- , S 3 O 2- , SSNO - , NO and RSS/RSeS.