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

► Extension of the alkylation chemistry of [Pt2(μ-S)2(PPh3)4] towards fluorinated alkyl halides. ► X-ray structure of [Pt2(μ-S)(μ-SCH2C6F5)(PPh3)4]BPh4·2C6H6 shows S⋯C6F5 π interaction. ► Interaction holds C6F5 group above the {Pt2S2} core, in contrast to benzyle analogue.