Please use this identifier to cite or link to this item:
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.
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
ISSN: 0022328X
DOI: 10.1016/j.jorganchem.2006.02.020
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.


checked on Jan 14, 2019


checked on Jan 7, 2019

Page view(s)

checked on Jan 11, 2019

Google ScholarTM



Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.