[Pt2(μ-SAz)(μ-S)]2+ (SAz = azolium thiolate) dication as an unusual source for quadruply bridging sulfide in [Ag2Pt2(μ-SAz)(μ4-S)]3+

Abstract

Functionalisation of the {Pt₂(μ-S)₂} core of [Pt₂(μ-S)₂(PPh₃)₄] by imidazolium, benzimidazolium and thiazolium salts results in a series of cationic complexes with mixed-bridging ligands of azolium thiolate and sulfide. The complex [Pt₂(μ-S)(μ-SCH₂CH₂C₃H₃N₂CH₃)(PPh₃)₄][PF₆]₂ reacts readily with Ag(OTf) (OTf = triflate) to give [Pt₂(μ-SAg₂CF₃SO₄H₂)(μ-SCH₂CH₂C₃H₃N₂CH₃)(PPh₃)₄][PF₆]₃. X-ray crystallographic analysis was carried out on [Pt₂(μ-S)(μ-SCH₂CH₂C₃H₃N₂CH₃)(PPh₃)₄][PF₆]₂, [Pt₂(μ-S)(μ-S(CH₂)₃C₇H₅NS)(PPh₃)₄][PF₆]₂, [Pt₂(μ-S)(μ-SCH₂CH₂C₃H₃N₂CH₃)(dppy)₄][PF₆]₂, [Pt₂(μ-S)(μ-SCH₂CH₂C₃H₃N₂CH₃)(dppf)₄][PF₆]₂, [Pt₂(μ-SAg₂CF₃SO₄H₂)(μ-SCH₂CH₂C₃H₃N₂CH₃)(PPh₃)₄][PF₆]₃ and [Pt₂(μ-SCH₃)(μ-SCH₂CH₂C₃H₃N₂CH₃)(PPh₃)₄][PF₆]₃. The complex [Pt₂(μ-SAg₂CF₃SO₄H₂)(μ-SCH₂CH₂C₃H₃N₂CH₃)(PPh₃)₄][PF₆]₃ reveals an unusual quadruply bridging sulfide, whose presence demonstrates an unexpected ability for the unsubstituted sulfide in the [Pt₂(SR)(S)] core to capture silver moieties.