The normally robust monoalkylated complexes [Pt2(µ-S)(µ-SR)(PPh3)4]⁺ can be activated towards further alkylation. Dialkylated complexes [Pt2(µ-SR)2(Pâ P)2]²⁺ (Pâ P = 2 à PPh3, Ph2P(CH2)3PPh2) can be stabilized and isolated by the use of electron-rich and aromatic halogenated substituents R [e.g. 3-(2-bromoethyl)indole and 2-bromo-4â ²-phenylacetophenone] and 1,3-bis(diphenylphosphino)propane [Ph2P(CH2)3PPh2 or dppp] which enhances the nucleophilicity of the {Pt2(µ-S)2} core. This strategy led to the activation of [Pt2(µ-S)(µ-SR)(PPh3)4]⁺ towards Râ X as well as isolation and crystallographic elucidation of [Pt2(µ-SC10H10N)2(PPh3)4](PF6)2 (2a), [Pt2(µ-SCH2C(O)C6H4C6H5)2(PPh3)4](PF6)2 (2b), and a range of functionalized-thiolato bridged complexes such as [Pt2(µ-SR)2(dppp)2](PF6)2 [R = â CH2C6H5 (8a), â CH2CHCH2 (8b) and â CH2CN (8c)]. The stepwise alkylation process is conveniently monitored by Electrospray Ionisation Mass Spectrometry, allowing for a direct qualitative comparison of the nucleophilicity of [Pt2(µ-S)2(Pâ P)2], thereby guiding the bench-top synthesis of some products observed spectroscopically.