A combinatorial-like probe on the reactivity of the {Pt2S2} core of Pt2(PPh3)4(μ-S)2 by electrospray mass spectrometry. Synthesis and structures of novel heterometallic sulfide aggregates of gold(III), mercury(II), and tin(IV) with platinum(II)

Electrospray mass spectrometry (ESMS) provides a rapid and convenient technique for probing the nucleophilicity of the {Pt2S2} “butterfly” core. Positive-ion electrospray mass spectra have been recorded for a wide array of aggregates incorporating various metallo-fragments into the Pt2(PPh3)4(μ-S)21 moiety. Such combinatorial-like screening allowed a large number of different metal–sulfur interactions to be studied and the resultant heterometallic aggregates postulated. Such postulations were subsequently confirmed by synthetic studies and single-crystal X-ray crystallographic analyses. This approach helped to minimize the “wastage” by focusing on the synthesis of aggregates that were supported by the ESMS evidence. It has resulted in the isolation of a series of novel aggregates such as {AuIIIPt2S2}, {HgIIPt2S2}, and {SnIVPt2S2} in good lab-scale yields. It also led to the trapping and characterization of the monoprotonated product of 1, which has eluded isolation.