Synthetic, Structural, Electrochemical, and Theoretical Studies of Heterometallic Aggregates with a [Pt₂(μ-S)₂M] Core (M = Hg, Au)

Novel electroactive multimetallic compounds based on the {Pt2(μ2-S)2M} core, viz. [Pt2(PPh3)4(μ3-S)2HgFc]PF6 (1) [Fc = (η5-C5H4)Fe(η5-C5H5)] and [Pt2(PPh3)4(μ3-S)2Hg2Fc‘](PF6)2 (2) [Fc‘ = Fe(η5-C5H4)2], have been synthesized under the guide of electrospray mass spectrometry. The electrochemistry of these ferrocene funtionalized compounds together with the reported [Pt2(PPh3)4(μ3-S)2HgPPh3](PF6)2 (3), [Pt2(PPh3)4(μ2-S)(μ3-S)HgPh]PF6 (4), and [Pt2(PPh3)4(μ2-S)(μ3-S)AuPPh3]PF6 (5) have been investigated using cyclic voltammetry and DFT calculations. These results point to a prominent ligand-based oxidation.