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.