Nonheme binuclear transition metal complexes with hydrosulfide and polychalcogenides

Abstract

The intriguing chemistry of chalcogen (S, Se) containing ligands and their capability to bridge multiple metal centres have resulted in a plethora of reports on transition metal complexes featuring hydrosulfide...

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

“…The synthesis of binuclear transition metal-polychalcogenido complexes via two-electron redox reaction between thiolates and S 8 /[Se] would require the presence of two coordinated thiolates in the starting transition metal–thiolate complex. , However, the treatment of H-HPTP·4HClO 4 with Zn(II) salt in the presence of Et 3 N in EtOH followed by the addition of RS – (R = Me, Ph) allowed the isolation of the monothiolate bridged binuclear Zn(II) complexes, [Zn 2 (HPTP)(μ-SR)] 2+ (R = Me, 1a ; Ph, 1b ; Scheme ). Use of excess thiolates in the above-mentioned reaction could not provide the desired bis(thiolate)Zn(II) complex and instead, produced only 1a and 1b .…”

“…Yield of the organic product = response factor ×100% = (area under the curve of organic product)/ (area under the curve of mesitylene) × 100%. 63,64 However, the treatment of H-HPTP•4HClO 4 82 with Zn(II) salt in the presence of Et 3 N in EtOH followed by the addition of RS − (R = Me, Ph) allowed the isolation of the monothiolate bridged binuclear Zn(II) complexes, [Zn 2 (HPTP)(μ-SR)] 2+ (R = Me, 1a; Ph, 1b; Scheme 1). Use of excess thiolates in the above-mentioned reaction could not provide the desired bis(thiolate)Zn(II) complex and instead, produced only 1a and 1b.…”

“…, 63 an alternative synthetic route involving a two-electron redox reaction between coordinated thiolates and exogenous elemental chalcogens (S 8 , [Se]) has recently been introduced by us. 63−65 In contrast to the large number of reports on the synthesis and molecular structures of transition metal polychalcogenido complexes, their reactivity is relatively less explored.…”

“…Readily accessible oxidation states of -II to + VI for sulfur and selenium, biological implications of sulfur and selenium derived anions and the ability of these anions to bridge multiple metal centers have paved the way for the development of transition metals chemistry of S n 2– and Se n 2– ligands. While the synthetic methods reported in the literature for the generation of transition metal-polychalcogenido complexes mainly involved either the reaction of elemental chalcogens with low valent transition metals or the reaction of transition metal salts with S n 2– /Se n 2– , an alternative synthetic route involving a two-electron redox reaction between coordinated thiolates and exogenous elemental chalcogens (S 8 , [Se]) has recently been introduced by us. − In contrast to the large number of reports on the synthesis and molecular structures of transition metal polychalcogenido complexes, their reactivity is relatively less explored. Available literature reports on the reactivity of transition metal-polychalcogenido complexes mainly include the reaction of the coordinated polychalcogenido chains with phosphines, − alkenes and alkynes, ,− carbon disulfide (CS 2 ), ,, sulfenyl chlorides (e.g., C 6 H 4 (SCl) 2 ), Se 2 Cl 2 , S 8 /[Se], 64 alkylating agents, as well as sulfur transfer reactions .…”