Mass spectrometry-directed synthesis of ‘early–late’ sulfide-bridged heterobimetallic complexes from the metalloligand [Pt2(PPh3)4(μ-S)2] and oxo compounds of vanadium(V), molybdenum(VI) and uranium(VI)

The metalloligand [Pt2(PPh3)4(μ-S)2] has been found to react with the transition metal oxo compounds, ammonium metavanadate, sodium molybdate, and the actinide complex uranyl nitrate to give sulfide-bridged heterobimetallic complexes [Pt2(PPh3)4(μ3-S)2VO(OMe)2]+, [Pt2(PPh3)4(μ3-S)2MoO2(OMe)]+, and [Pt2(PPh3)4(μ3-S)2UO2(η2-NO3)2], respectively. Electrospray mass spectrometry (ESMS) was used to probe the reactivity of [Pt2(PPh3)4(μ-S)2] and thus identify likely targets for isolation and characterization. ESMS has also been used to investigate fragmentation pathways of the new species. No bimetallic species were detected with hydrated La(NO3)3 or Th(NO3)4, or with the lanthanide shift reagent Eu(fod)3 (fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate). X-Ray crystal structure determinations have been carried out on [Pt2(PPh3)4(μ3-S)2VO(OMe)2]+, 2, (as its hexafluorophosphate salt) and [Pt2(PPh3)4(μ3-S)2UO2(η2-NO3)2], 4. The vanadium atom of 2 has a distorted square pyramidal geometry, while the uranium in 4 has the expected linear dioxo coordination geometry, with two bidentate nitrates and a bidentate {Pt2S2} moiety.

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