Please use this identifier to cite or link to this item: https://doi.org/10.1016/j.jorganchem.2006.02.020
Title: Moderating the nucleophilicity of the sulfide ligands in the dinuclear {Pt2S2} metalloligand system using triphenylarsine
Authors: Jeram, S.
Henderson, W.
Nicholson, B.K.
Hor, T.S.A. 
Keywords: Arsine ligands
Electrospray mass spectrometry
Platinum complexes
Sulfide ligands
Issue Date: 1-Jun-2006
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
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.
Source Title: Journal of Organometallic Chemistry
URI: http://scholarbank.nus.edu.sg/handle/10635/94292
ISSN: 0022328X
DOI: 10.1016/j.jorganchem.2006.02.020
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