Further studies on the dialkylation chemistry of [Pt₂(μ-S)₂(PPh₃)₄] with activated alkyl halides RC(O)CH₂X (X = Cl, Br)

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dc.contributor.authorUjam, Oguejiofo Theophilus
dc.contributor.authorHenderson, William
dc.contributor.authorNicholson, Brian K.
dc.contributor.authorHor, T.S. Andy
dc.date.accessioned2011-07-05T22:53:24Z
dc.date.available2011-07-05T22:53:24Z
dc.date.issued2011
dc.description.abstractFurther studies have been carried out into the reactivity of [Pt₂(μ-S)₂(PPh₃)₄] towards a range of activated alkylating agents of the type RC(O)CH₂X (R = organic moiety e.g. phenyl, pyrenyl; X = Cl, Br). Alkylation of both sulfide centres is observed for PhC(O)CH₂Br, 3-(bromoacetyl)coumarin [CouC(O)CH₂Br], and 1-(bromoacetyl)pyrene [PyrC(O)CH2Br], giving dications [Pt₂{μ-SCH₂C(O)R}₂ (PPh₃)₄] ²⁺, isolated as their PF₆⁻ salts. The X-ray structure of [Pt₂{μ-SCH₂C(O)Ph}₂ (PPh₃)₄](PF₆) ₂ shows the presence of short Pt•••O contacts. In contrast, the corresponding chloro compounds [typified by PhC(O)CH₂Cl] and imino analogues [e.g. PhC(NOH)CH₂Br] do not dialkylate [Pt₂ (μ-S)₂(PPh₃)₄]. The ability of PhC(O)CH₂Br to dialkylate [Pt₂(μ-S)₂(PPh₃)₄] allows the synthesis of new mixed-alkyl dithiolate derivatives of the type [Pt₂{μ-SCH₂C(O)Ph}(μ-SR)(PPh₃)₄]²⁺ (R = Et or n-Bu), through alkylation of in situ-generated monoalkylated compounds [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ (from [Pt₂(μ-S)₂(PPh₃)₄] and excess RBr). In these heterodialkylated systems ligand replacement of PPh₃ occurs by the bromide ions in the reaction mixture forming monocations [Pt₂{μ-SCH₂C(O)Ph}(μ-SR)(PPh₃)₃Br]⁺. This ligand substitution can be easily suppressed by addition of PPh₃ to the reaction mixture. The complex [Pt₂{μ-SCH₂C(O)Ph}(μ-SBu)(PPh₃)₄]²⁺ was crystallographically characterised. X-ray crystal structures of the bromide-containing complexes [Pt₂{μ-SCH₂C(O)Ph}(μ-SR)(PPh₃)₃Br]+ (R = Et, Bu) are also reported. In both structures the coordinated bromide is trans to the SCH₂C(O)Ph ligand, which adopts an axial position, while the ethyl and butyl substituents adopt equatorial positions, in contrast to the structures of the dialkylated complexes [Pt₂{μ-SCH₂C(O)Ph}₂(PPh₃)₄]²⁺ and [Pt₂{μ-SCH₂C(O)Ph}(μ-SBu)(PPh₃)₄]²⁺ (and many other known analogues) where both alkyl groups adopt axial positions.en_NZ
dc.format.mimetypeapplication/pdf
dc.identifier.citationUjam, O.T., Henderson, W., Nicholson, B.K. & Hor, T.S.A. (2011). Further studies on the dialkylation chemistry of [Pt₂(μ-S)₂(PPh₃)₄] with activated alkyl halides RC(O)CH₂X (X = Cl, Br). Inorganica Chimica Acta, available online 21 June 2011.en_NZ
dc.identifier.doi10.1016/j.ica.2011.06.023en_NZ
dc.identifier.urihttps://hdl.handle.net/10289/5455
dc.language.isoen
dc.publisherElsevier BVen_NZ
dc.relation.isPartOfInorganica Chimica Actaen_NZ
dc.relation.urihttp://www.sciencedirect.com/science/article/pii/S0020169311005226en_NZ
dc.rightsThis is an author’s accepted version of an article published in the journal: Inorganica Chimica Acta. © 2011 Elsevier.en_NZ
dc.subjectDinuclear platinum complexesen_NZ
dc.subjectThiolate complexesen_NZ
dc.subjectalkylation reactionsen_NZ
dc.subjectligand substitutionen_NZ
dc.subjectelectrospray ionisation mass spectrometryen_NZ
dc.subjectX-ray crystal structuresen_NZ
dc.titleFurther studies on the dialkylation chemistry of [Pt₂(μ-S)₂(PPh₃)₄] with activated alkyl halides RC(O)CH₂X (X = Cl, Br)en_NZ
dc.typeJournal Articleen_NZ
pubs.begin-page255en_NZ
pubs.elements-id36073
pubs.end-page263en_NZ
pubs.issue1en_NZ
pubs.volume376en_NZ
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