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

TitleModerating the nucleophilicity of the sulfide ligands in the dinuclear {Pt2S2} metalloligand system using triphenylarsine
Authors
KeywordsSulfide ligands
Platinum complexes
Electrospray mass spectrometry
Arsine ligands
Issue Date2006
Citation
Journal of Organometallic Chemistry, 2006, v. 691, n. 12, p. 2827-2838 How to Cite?
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. © 2006 Elsevier B.V. All rights reserved.
Persistent Identifierhttp://hdl.handle.net/10722/219366
ISSN
2015 Impact Factor: 2.336
2015 SCImago Journal Rankings: 0.732

 

DC FieldValueLanguage
dc.contributor.authorJeram, Sunita-
dc.contributor.authorHenderson, William-
dc.contributor.authorNicholson, Brian K.-
dc.contributor.authorHor, T. S Andy-
dc.date.accessioned2015-09-23T02:56:53Z-
dc.date.available2015-09-23T02:56:53Z-
dc.date.issued2006-
dc.identifier.citationJournal of Organometallic Chemistry, 2006, v. 691, n. 12, p. 2827-2838-
dc.identifier.issn0022-328X-
dc.identifier.urihttp://hdl.handle.net/10722/219366-
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. © 2006 Elsevier B.V. All rights reserved.-
dc.languageeng-
dc.relation.ispartofJournal of Organometallic Chemistry-
dc.subjectSulfide ligands-
dc.subjectPlatinum complexes-
dc.subjectElectrospray mass spectrometry-
dc.subjectArsine ligands-
dc.titleModerating the nucleophilicity of the sulfide ligands in the dinuclear {Pt2S2} metalloligand system using triphenylarsine-
dc.typeArticle-
dc.description.natureLink_to_subscribed_fulltext-
dc.identifier.doi10.1016/j.jorganchem.2006.02.020-
dc.identifier.scopuseid_2-s2.0-33646371690-
dc.identifier.volume691-
dc.identifier.issue12-
dc.identifier.spage2827-
dc.identifier.epage2838-

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