| 136705-10-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 136705-10-7
• 化学式: C₁₃₈H₁₁₈Au₂O₂P₁₀Pt₄*2F₆P
• 分子量: 3582.37
• InChiKey: QRQAWBMOGFCMSO-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  triphenylphosphinegold(I) nitrate 、 {Pt(μ-H)(μ-CO)2(μ-Ph2PCH2PPh2)3(Ph2PCH2PPh2)}PF6 在 NH₄PF₆ 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Synthesis, structure, and properties of a tetranuclear platinum cluster cation

  摘要：

  The reaction of [Pt(O2CCF3)2(dppm)] (dppm = Ph2PCH2PPh2) with CO/H2O at 100-degrees-C gives the 58-electron cluster cation [Pt4(mu-H)(mu-CO)2(mu-dppm)3(dppm-P)]+ (1). The structure of 1[PF6] has been determined crystallographically (space group Pcab (No. 61), a = 21.120 (6) angstrom, b = 28.962 (4) angstrom, c = 31.026 (4) angstrom, Z = 8) and shown to contain a Pt4 core in a butterfly geometry. The cluster cation can be considered to be derived from a triangular Pt3(mu-dppm)3 unit, with one edge bridged above by a Pt(CO)2(dppm-P) unit and below by a proton. Variable-temperature H-1, C-13, P-31, and Pt-195 NMR spectra show that the cluster cation 1 is fluxional, and the detailed mechanism of this fluxionality has been elucidated by analysis of the coupling constants to Pt-195 in the slow- and fast-exchange regions. The cluster core of 1 is robust, but it can be decomposed by H+ or Ag+ to give the cluster cation [Pt3(mu-3-CO)(mu-dppm)3]2+. Methyl isocyanide displaces the carbonyl ligands of 1 to give [Pt4(mu-H)(mu-CNMe)2(mu-dppm)3(dppm-P)]+ (4). The dppm-P ligand of 1 is easily oxidized by O2 or H2O2 to give [Pt4(mu-H)(mu-CO)2(mu-dppm)3(Ph2PCH2P(= O)Ph2)]+ (5) and by S8 or H2S to give [Pt4(mu-H)(mu-CO)2(mu-dppm)3(Ph2PCH2P(= S)Ph2)]+ (6). The reagents Ph3PAu+ and [Pt(O2CCF3)2(dppm)] react with 1 to give [Pt4(mu-AuPPh3)(mu-CO)2(mu-dppm)3(dppm-AuPPh3)][PF6]2 (7[PF6]2) and [Pt4(mu-H)(mu-CO)2(mu-dppm)3{dppm-Pt(O2CCF3)(dppm)}][PF6]2 (8[PF6]2), respectively, by coordination to the dppm-P ligand and, in the case of the gold reagent, by isolobal substitution of LAu+ for H+. These complexes have been characterized by multinuclear NMR methods.

  DOI：

  10.1021/om00057a026