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

Electrospray mass spectrometry (ESMS) provides a rapid and convenient techn ique for probing the nucleophilicity of the {Pt2S2} "butterfly" core. Posit ive-ion electrospray mass spectra have been recorded for a wide array of ag gregates incorporating various metallo-fragments into the Pt-2(PPh3)(4)(mu -S)(2) 1 moiety. Such combinatorial-like screening allowed a large number o f different metal-sulfur interactions to be studied and the resultant heter ometallic aggregates postulated. Such postulations were subsequently confir med by synthetic studies and single-crystal X-ray crystallographic analyses . This approach helped to minimize the "wastage" by focusing on the synthes is of aggregates that were supported by the ESMS evidence. It has resulted in the isolation of a series of novel aggregates such as {(AuPt2S2)-Pt-III} , {(HgPt2S2)-Pt-II}, and {(SnPt2S2)-Pt-IV} in good lab-scale yields. It als o led to the trapping and characterization of the monoprotonated product of 1, which has eluded isolation.