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dc.contributor.authorJeram, Sunitaen_US
dc.contributor.authorHenderson, Williamen_US
dc.contributor.authorNicholson, Brian K.en_US
dc.contributor.authorHor, T.S. Andyen_US
dc.identifier.citationJeram, S., Henderson, W., Nicholson, B.K. & Hor, T.S.A. (2006). Moderating the nucleophilicity of the sulfide ligands in the dinuclear {Pt₂S₂} metalloligand system using triphenylarsine. Journal of Organometallic Chemistry, 691(12), 2827-2838.en_US
dc.description.abstractReaction 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.en_US
dc.publisherElsevier S.A.en_NZ
dc.rightsThis article is published in the Journal of Organometallic Chemistry, (c) 2006 Elsevier B.V.en_US
dc.subjectArsine ligandsen_US
dc.subjectSulfide ligandsen_US
dc.subjectPlatinum complexesen_US
dc.subjectElectrospray mass spectrometryen_US
dc.titleModerating the nucleophilicity of the sulfide ligands in the dinuclear {Pt₂S₂} metalloligand system using triphenylarsineen_US
dc.typeJournal Articleen_US
dc.relation.isPartOfJournal of Organometallic Chemistryen_NZ

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