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      Ligand functionalization, reactivity, and transformation at the selenide centers of [Pt₂(μ-Se)₂(PPh₃)₄] with organic halides

      Yeo, Jeremy S.L.; Vittal, Jagadese J.; Henderson, William; Hor, T.S. Andy
      DOI
       10.1021/om020114e
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      Yeo, J. S. L., Vittal, J. J., Henderson, W. & Hor, T. S. A. (2002). Ligand functionalization, reactivity, and transformation at the selenide centers of [Pt₂(μ-Se)₂(PPh₃)₄] with organic halides. Journal of Organometallics, 21(14), 2944-2949.
      Permanent Research Commons link: https://hdl.handle.net/10289/2886
      Abstract
      The selenium centers of [Pt₂(μ-Se)₂(PPh₃)₄] are subject to electrophilic attack from various organic halides. Reactions with MeI, n-BuCl, α,α⁶-dichloro-p-xylene, and α,α⁶-dichloro-o-xylene give [Pt₂(μ-Se)(μ-SeMe)(PPh₃)₄]⁺, [Pt₂(μ-Se)(μ-SeBu)(PPh₃)₄]⁺, [Pt₂(μ-Se)(μ-SeCH₂C₆H₄CH₂Cl)(PPh₃)₄]⁺, and [Pt₂(μ-SeCH₂C₆H₄CH₂Se)(PPh₃)₄]²⁺, respectively, preserving the dinuclear core and giving rise to new selenium-derivatized ligand complexes. Reaction with oxalyl chloride gives [Pt(η²-Se₂C₂O₂-Se,Se⁶)(PPh₃)₂], leading to the disintegration of the core to a mononuclear complex supported by a new chelating selenium donor ligand. Reactions with malonyl chloride and succinyl chloride give [(COCH₂COCl)Se]₂ and [(COCH₂CH₂COCl)Se]₂ respectively, leading to complex disintegration and liberation of new selenium materials. The crystal structures of the aggregates [Pt₂(μ-Se)(μ-SeMe)(PPh₃)₄][PF₆], [Pt₂(μ₃-Se)₂(PPh₃)₄(CH₂C₆H₄CH₂)][PF₆]₁.₂₅[Cl]₀.₇₅, and [Pt(η²-Se₂C₂O₂-Se,Se⁶)(PPh₃)₂] are described. The potential of using [Pt₂(μ-Se)₂(PPh₃)₄] as a source for metal-assisted synthesis of new and unusual organoselenium compounds is discussed.
      Date
      2002
      Type
      Journal Article
      Publisher
      American Chemical Society
      Rights
      This article is published in the Journal of Organometallics. (c) 2002 American Chemical Society
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      • Science and Engineering Papers [3019]
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