Moderating the nucleophilicity of the sulfide ligands in the dinuclear {Pt2S2} metalloligand system using triphenylarsine

Reaction of cis-[PtCl2(AsPh3)2] with excess sodium sulfide in benzene gave the triphenylarsine analogue of the well-known metalloligand [Pt2(μ-S)2(PPh3)4] as an orange solid.The compound was characterised by detailed mass spectrometry studies, and by conversion to various alkylated and metallated derivatives.The sulfide ligands in [Pt2(μ-S)2(AsPh3)4] are less basic than the triphenylphosphine analogue, and the complex gives a relatively weak [M+H]+ ion in the positive-ion electrospray (ESI) mass spectrum, compared with the phosphine analogue.Methylation of an equimolar mixture of [Pt2(μ-S)2(PPh3)4] and [Pt2(μ-S)2(AsPh3)4] with MeI gave the species [Pt2(μ-S)(μ-SMe)(AsPh3)4]+ and [Pt2(μ-SMe)2(PPh3)3I]+, indicating a reduced tendency for the sulfide of [Pt2(μ-S)(μ-SMe)(AsPh3)4]+ to undergo alkylation.The lability of the arsine ligands is confirmed by the reaction of an equimolar mixture of [Pt2(μ-S)2(PPh3)4] and [Pt2(μ-S)2(AsPh3)4] with n-butyl chloride, giving [Pt2(μ-S)(μ-SBu)(EPh3)4]+ (E = P, As), which with Me2SO4 gave a mixture of [Pt2(μ-SMe)(μ-SBu)(PPh3)4]2+ and [Pt2(μ-SMe)(μ-SBu)(AsPh3)3Cl]+.Reactivity towards 1,2-dichloroethane follows a similar pattern.The formation and ESI MS detection of mixed phosphine–arsine {Pt2S2} species of the type[Pt2(μ-S)2(AsPh3)n(PPh3)4−n] is also discussed. Coordination chemistry of [Pt2(μ-S)2(AsPh3)4] towards a range of metal-chloride substrates, forming sulfide-bridged trinuclear aggregates, has also been probed using ESI MS, and found to be similar to the phosphine analogue. The X-ray crystal structure of [Pt2(μ-S)2(AsPh3)4Pt(cod)](PF6)2 (cod = 1,5-cyclo-octadiene) has been determined for comparison with the (previously reported) triphenylphosphine analogue. ESI MS is a powerful tool in exploring the chemistry of this system; in some cases the derivatising agent p-bromobenzyl bromide is used to convert sparingly soluble and/or poorly ionising {Pt2S2} species into soluble, charged derivatives for MS analysis.

The complex [Pt2(μ-S)2(AsPh3)4], which is the triphenylarsine analogue of the extensively studied metalloligand [Pt2(μ-S)2(PPh3)4], has been synthesised and its chemistry studied, primarily using the technique of electrospray ionisation mass spectrometry.The results point towards a complex that contains somewhat less basic and nucleophilic sulfide centres, that together with the presence of labile arsine ligands modifies the chemistry of this complex towards alkylating agents.Figure optionsDownload as PowerPoint slide