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dc.contributor.authorUjam, Oguejiofo Theophilus
dc.contributor.authorDevoy, Sarah M.
dc.contributor.authorHenderson, William
dc.contributor.authorNicholson, Brian K.
dc.contributor.authorHor, T.S. Andy
dc.coverage.spatialEnglanden_NZ
dc.date.accessioned2012-10-29T01:07:43Z
dc.date.available2012-10-29T01:07:43Z
dc.date.copyright2012
dc.date.issued2012
dc.identifier.citationUjam, O. T., Devoy, S. M., Henderson, W., Nicholson, B. K., & Hor, T. S. A. (2012). A novel structural rearrangement reaction of dialkylated derivatives of [Pt ₂ (μ-S) ₂ (PPh ₃) ₄] involving Pt-C bond formation. Dalton Transactions, 41(41), 12773-12780.en_NZ
dc.identifier.issn1477-9226
dc.identifier.urihttps://hdl.handle.net/10289/6748
dc.description.abstractReaction of [Pt ₂ (μ-S) ₂ (PPh ₃) ₄] with the dialkylating agents ClCH ₂ C(O)CH ₂ Cl or ClCH ₂ C(NNHC(O)NH ₂)CH ₂ Cl gives the dicationic di-μ-thiolate complexes [Pt ₂ {μ-SCH ₂ C(O)CH ₂ S)(PPh ₃) ₄] ²⁺ or [Pt ₂ {μ-SCH ₂ C(NNHC(O)NH ₂)CH ₂ S} (PPh ₃) ₄] ²⁺, isolated as BPh ₄ ⁻ salts and characterised by ESI mass spectrometry, NMR spectroscopy and single-crystal X-ray crystallography. Treatment of the complex [Pt 2{μ-SCH 2C(O)CH 2S)(PPh₃) ₄] ²⁺, which contains a [6.6.4] bicyclic system, with hydroxide ions results in deprotonation of a CH 2 group and rearrangement of the resulting monocation, giving [Pt ₂ (μ-SCH ₂ C(O)CHS}(PPh ₃) ₄] ⁺, isolated as its PF ₆ ⁻ salt. An X-ray structure determination shows the complex to have a novel rearranged [6.5.5] bicyclic system containing a Pt-S-Pt-S-C five-membered ring with a Pt-C bond. The alkyl ligand has a high trans-influence, manifest in a long trans Pt-P bond and small 1J(PtP) coupling constant to the trans PPh 3 ligand. Reaction of [Pt ₂ (μ-S) ₂ (PPh ₃) ₄] with the 2,4-dinitrophenylhydrazone derivative of 1,3-dichloroacetone leads to the closely related complex [Pt ₂ {μ-SCH ₂ C(NNHAr)CHS} (PPh ₃) ₃Cl] [Ar = C ₆H ₃ (NO ₂) ₂] in which a PPh ₃ ligand is substituted by a chloride.en_NZ
dc.language.isoen
dc.publisherRoyal Society of Chemistryen_NZ
dc.relation.ispartofDalton Transactions
dc.titleA novel structural rearrangement reaction of dialkylated derivatives of [Pt ₂ (μ-S) ₂ (PPh ₃) ₄] involving Pt-C bond formationen_NZ
dc.typeJournal Articleen_NZ
dc.identifier.doi10.1039/c2dt31637den_NZ
dc.relation.isPartOfDalton Transactionsen_NZ
pubs.begin-page12773en_NZ
pubs.elements-id38061
pubs.end-page12780en_NZ
pubs.issue41en_NZ
pubs.volume41en_NZ


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