Dinuclear platinum(II) sulfide–thiolate complexes [Pt2(μ-S)(μ-SR)(PPh3)4]+ containing fluorinated substituents and the identification of a S⋯C6F5 π interaction in the crystal structure of [Pt2(μ-S)(μ-SCH2C6F5)(PPh3)4]BPh4·2C6H6

Reactions of the platinum(II) sulfido complex [Pt2(μ-S)2(PPh3)4] with the alkyl iodides ICH2CH2(CF2)nCF3 (n = 3, 7) gives good yields of the monoalkylated products [Pt2(μ-S){μ-SCH2CH2(CF2)nCF3}(PPh3)4]+, which were isolated as PF 6 - or BPh 4 - salts, and characterised by ESI mass spectrometry, NMR spectroscopy and elemental analysis. The complex [Pt2(μ-S){μ-SCH2CH2(CF2)nCF3}(PPh3)4]+ appears to have normal reactivity for this type of complex, namely reaction with Ph3PAuCl to give [Pt2(μ-SAuPPh3){μ-SCH2CH2(CF2)nCF3}(PPh3)4]2+, and reaction with Me2SO4 to give [Pt2(μ-SMe){μ-SCH2CH2(CF2)nCF3}(PPh3)4]2+. Reaction of [Pt2(μ-S)2(PPh3)4] with C6F5CH2Br gave [Pt2(μ-S)(μ-SCH2C6F5)(PPh3)4]+, isolated as its BPh 4 - salt, and characterised by NMR spectroscopy and a single-crystal X-ray structure determination. The C6F5 group lies above the {Pt2S2} core of the complex as a result of a S⋯C6F5 π interaction, in contrast to the published structure of [Pt2(μ-S)(μ-SCH2C6H5)(PPh3)4]PF6, where the C6H5 group projects away from the {Pt2S2} core.