The arylation of [Pt2(μ-S)2(PPh3)4]

Routes to the synthesis of the mixed sulfide-phenylthiolate complex [Pt2(μ-S)(μ-SPh)(PPh3)4]+ have been explored; reaction of [Pt2(μ-S)2(PPh3)4] with excess Ph2IBr proceeds readily to selectively produce this complex, which was structurally characterised as its PF6− salt. Reactions of [Pt2(μ-S)2(PPh3)4] with other potent arylating reagents (1-chloro-2,4-dinitrobenzene and 1,5-difluoro-2,4-dinitrobenzene) also produce the corresponding nitroaryl-thiolate complexes [Pt2(μ-S){μ-SC6H2(NO2)2X}(PPh3)4]+ (X = H, F). The complex [Pt2(μ-S)(μ-SPh)(PPh3)4]+ reacts with Me2SO4 to produce the mixed alkyl/aryl bis-thiolate complex [Pt2(μ-SMe)(μ-SPh)(PPh3)4]2+, but corresponding reactions with the nitroaryl-thiolate complexes are plagued by elimination of the nitroaryl group and formation of [Pt2(μ-SMe)2(PPh3)4]2+. [Pt2(μ-S)(μ-SPh)(PPh3)4]+ also reacts with Ph3PAuCl to give [Pt2(μ-SAuPPh3)(μ-SPh)(PPh3)4]2+.