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      Thallium(III) complexes of the metalloligands [Pt₂(μ-S)₂(PPh₃)₄] and [Pt₂(μ-Se)₂(PPh₃)₄]

      Rose, Sarah L.; Henderson, William; Nicholson, Brian K.; Hor, T.S. Andy
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      DOI
       10.1016/j.ica.2009.09.045
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      Rose, S. L., Henderson, W., Nicholson, B. K. & Hor, A. T. S. (2009). Thallium(III) complexes of the metalloligands [Pt₂(μ-S)₂(PPh₃)₄] and [Pt₂(μ-Se)₂(PPh₃)₄]. Inorganica Chimica Acta, 362(15), 5237-5244.
      Permanent Research Commons link: https://hdl.handle.net/10289/3248
      Abstract
      Reactions of [Pt₂(μ-S)₂(PPh₃)₄] with the diarylthallium(III) bromides Ar₂TlBr [Ar = Ph and p-ClC₆H₄] in methanol gave good yields of the thallium(III) adducts [Pt₂(μ-S)₂(PPh₃)4TlAr₂]⁺, isolated as their BPh₄⁻ salts. The corresponding selenide complex [Pt₂(μ-Se)₂(PPh₃)₄TlPh₂]BPh₄ was similarly synthesised from [Pt₂(μ-Se)₂(PPh₃)₄], Ph₂TlBr and NaBPh₄. The reaction of [Pt₂(μ-S)₂(PPh₃)₄] with PhTlBr₂ gave [Pt₂(μ-S)₂(PPh₃)₄TlBrPh]⁺, while reaction with TlBr₃ gave the dibromothallium(III) adduct [Pt₂(μ-S)₂(PPh₃)₄TlBr₂]⁺[TlBr₄]⁻. The latter complex is a rare example of a thallium(III) dihalide complex stabilised solely by sulfur donor ligands. X-ray crystal structure determinations on the complexes [Pt₂(μ-S)₂(PPh₃)₄TlPh₂]BPh₄, [Pt₂(μ-S)₂(PPh₃)₄TlBrPh]BPh₄ and [Pt₂(μ-S)₂(PPh₃)₄TlBr₂][TlBr₄] reveal a greater interaction between the thallium(III) centre and the two sulfide ligands on stepwise replacement of Ph by Br, as indicated by shorter Tl-S and Pt...Tl distances, and an increasing S-Tl-S bond angle. Investigations of the ESI MS fragmentation behaviour of the thallium(III) complexes are reported.
      Date
      2009
      Type
      Journal Article
      Publisher
      Elsevier B.V.
      Rights
      This is an author’s accepted version of an article published in the journal: Inorganica Chimica Acta. ©2009 Elsevier. Used with permission.
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