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dc.contributor.authorPham, Kristina
dc.contributor.authorHenderson, William
dc.contributor.authorNicholson, Brian K.
dc.contributor.authorHor, T.S. Andy
dc.date.accessioned2009-08-12T03:16:41Z
dc.date.available2009-08-12T03:16:41Z
dc.date.issued2007
dc.identifier.citationPham, K., Henderson, W., Nicholson, B.K. & Hor, T.S.A. (2007). Tuning the sulfur–heterometal interaction in organolead(IV) complexes of [Pt₂(μ-S)₂(PPh₃)₄]. Journal of Organometallic Chemistry, 692(22), 4933-4942.en
dc.identifier.urihttps://hdl.handle.net/10289/2813
dc.description.abstractReactions of [Pt₂(μ-S)₂(PPh₃)₄] with Ph₃PbCl, Ph₂PbI₂, Ph₂PbBr₂ and Me₃PbOAc result in the formation of bright yellow to orange solutions containing the cations [Pt₂(μ-S)₂(PPh₃)₄PbR₃]⁺ (R₃ = Ph₃, Ph₂I, Ph₂Br, Me₃) isolated as PF₆⁻ or BPh₄⁻ salts. In the case of the Me₃Pb and Et₃Pb systems, a prolonged reaction time results in formation of the alkylated species [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ (R = Me, Et). X-ray structure determinations on [Pt₂(μ-S)₂(PPh₃)₄PbMe₃]PF₆ and [Pt₂(μ-S)₂(PPh₃)₄PbPh₂I]PF₆ have been carried out, revealing different coordination modes. In the Me₃Pb complex, the (four-coordinate) lead atom binds to a single sulfur atom, while in the Ph₂PbI adduct coordination of both sulfurs results in a five-coordinate lead centre. These differences are related to the electron density on the lead centre, and indicate that the interaction of the heterometal centre with the {Pt₂S₂} metalloligand core can be tuned by variation of the heteroatom substituents. The species [Pt₂(μ-S)₂(PPh₃)₄PbR₃]⁺ display differing fragmentation pathways in their ESI mass spectra, following initial loss of PPh₃ in all cases; for R = Ph, loss of PbPh₂ occurs, yielding [Pt₂(μ-S)₂(PPh₃)₃Ph]⁺, while for R = Me, reductive elimination of ethane gives [Pt₂(μ-S)₂(PPh₃)₃PbMe]⁺, which is followed by loss of CH₄.en
dc.format.mimetypeapplication/pdf
dc.language.isoen
dc.publisherElsevier S.A.en_NZ
dc.rightsThis is an author’s accepted version of an article published in the Journal of Organometallic Chemistry. (c) 2007 Elsevier Science B. V.en
dc.subjectPlatinum complexesen
dc.subjectLead complexesen
dc.subjectSulfide ligandsen
dc.subjectCrystal structuresen
dc.subjectElectrospray mass spectrometryen
dc.titleTuning the sulfur–heterometal interaction in organolead(IV) complexes of [Pt₂(μ-S)₂(PPh₃)₄]en
dc.typeJournal Articleen
dc.identifier.doi10.1016/j.jorganchem.2007.07.010en
dc.relation.isPartOfJournal of Organometallic Chemistryen_NZ
pubs.begin-page4933en_NZ
pubs.editionOctoberen_NZ
pubs.elements-id32556
pubs.end-page4942en_NZ
pubs.issue22en_NZ
pubs.volume692en_NZ


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