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https://doi.org/10.1016/j.jorganchem.2006.02.020
DC Field | Value | |
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dc.title | Moderating the nucleophilicity of the sulfide ligands in the dinuclear {Pt2S2} metalloligand system using triphenylarsine | |
dc.contributor.author | Jeram, S. | |
dc.contributor.author | Henderson, W. | |
dc.contributor.author | Nicholson, B.K. | |
dc.contributor.author | Hor, T.S.A. | |
dc.date.accessioned | 2014-10-16T08:34:20Z | |
dc.date.available | 2014-10-16T08:34:20Z | |
dc.date.issued | 2006-06-01 | |
dc.identifier.citation | Jeram, S., Henderson, W., Nicholson, B.K., Hor, T.S.A. (2006-06-01). Moderating the nucleophilicity of the sulfide ligands in the dinuclear {Pt2S2} metalloligand system using triphenylarsine. Journal of Organometallic Chemistry 691 (12) : 2827-2838. ScholarBank@NUS Repository. https://doi.org/10.1016/j.jorganchem.2006.02.020 | |
dc.identifier.issn | 0022328X | |
dc.identifier.uri | http://scholarbank.nus.edu.sg/handle/10635/94292 | |
dc.description.abstract | 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. © 2006 Elsevier B.V. All rights reserved. | |
dc.description.uri | http://libproxy1.nus.edu.sg/login?url=http://dx.doi.org/10.1016/j.jorganchem.2006.02.020 | |
dc.source | Scopus | |
dc.subject | Arsine ligands | |
dc.subject | Electrospray mass spectrometry | |
dc.subject | Platinum complexes | |
dc.subject | Sulfide ligands | |
dc.type | Article | |
dc.contributor.department | CHEMISTRY | |
dc.description.doi | 10.1016/j.jorganchem.2006.02.020 | |
dc.description.sourcetitle | Journal of Organometallic Chemistry | |
dc.description.volume | 691 | |
dc.description.issue | 12 | |
dc.description.page | 2827-2838 | |
dc.description.coden | JORCA | |
dc.identifier.isiut | 000237995400026 | |
Appears in Collections: | Staff Publications |
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