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      Tuning the sulfur–heterometal interaction in organolead(IV) complexes of [Pt₂(μ-S)₂(PPh₃)₄]

      Pham, Kristina; Henderson, William; Nicholson, Brian K.; Hor, T.S. Andy
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      Henderson Pt2S2 lead.pdf
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      DOI
       10.1016/j.jorganchem.2007.07.010
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      Pham, 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.
      Permanent Research Commons link: https://hdl.handle.net/10289/2813
      Abstract
      Reactions 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.
      Date
      2007
      Type
      Journal Article
      Publisher
      Elsevier S.A.
      Rights
      This is an author’s accepted version of an article published in the Journal of Organometallic Chemistry. (c) 2007 Elsevier Science B. V.
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      • Science and Engineering Papers [3143]
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