[Pt2(mu-SAz)(mu-S)]2+ (SAz = azolium thiolate) dication as an unusual source for quadruply bridging sulfide in [Ag2Pt2(mu-SAz)(mu4-S)]3+.

Functionalisation of the {Pt(2)(mu-S)(2)} core of [Pt(2)(mu-S)(2)(PPh(3))(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 [Pt(2)(mu-S)(mu-SCH(2)CH(2)C(3)H(3)N(2)CH(3))(PPh(3))(4)]PF(6) reacts readily with Ag(OTf) (OTf = triflate) to give [Pt(2)(mu-SAg(2)CF(3)SO(4)H(2))(mu-SCH(2)CH(2)C(3)H(3)N(2)CH(3))(PPh(3))(4)]PF(6). X-ray crystallographic analysis was carried out on [Pt(2)(mu-S)(mu-SCH(2)CH(2)C(3)H(3)N(2)CH(3))(PPh(3))(4)]PF(6), [Pt(2)(mu-S)(mu-S(CH(2))(3)C(7)H(5)NS)(PPh(3))(4)]PF(6), [Pt(2)(mu-S)(mu-SCH(2)CH(2)C(3)H(3)N(2)CH(3))(dppy)(4)]PF(6), [Pt(2)(mu-S)(mu-SCH(2)CH(2)C(3)H(3)N(2)CH(3))(dppf)(4)]PF(6), [Pt(2)(mu-SAg(2)CF(3)SO(4)H(2))(mu-SCH(2)CH(2)C(3)H(3)N(2)CH(3))(PPh(3))(4)]PF(6) and [Pt(2)(mu-SCH(3))(mu-SCH(2)CH(2)C(3)H(3)N(2)CH(3))(PPh(3))(4)]PF(6). The complex [Pt(2)(mu-SAg(2)CF(3)SO(4)H(2))(mu-SCH(2)CH(2)C(3)H(3)N(2)CH(3))(PPh(3))(4)]PF(6) reveals an unusual quadruply bridging sulfide, whose presence demonstrates an unexpected ability for the unsubstituted sulfide in the [Pt(2)(SR)(S)] core to capture silver moieties.