[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+

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.