diphenylphosphanylmethyl(diphenyl)phosphane;platinum(2+);2,2,2-trifluoroacetate | 99642-82-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: diphenylphosphanylmethyl(diphenyl)phosphane;platinum(2+);2,2,2-trifluoroacetate
• CAS: 99642-82-7
• 化学式: C₂₉H₂₂F₆O₄P₂Pt
• 分子量: 805.509
• InChiKey: JXBLVWQMRVRTLN-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.32
• 重原子数：
  42.0
• 可旋转键数：
  6.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  diphenylphosphanylmethyl(diphenyl)phosphane;platinum(2+);2,2,2-trifluoroacetate 在 CO 作用下， 以 甲醇 、 水 为溶剂， 以97.5%的产率得到{Pt3(μ3-CO)(μ-dppm)3}(CF3CO2)2
  参考文献：
  名称：

  Ferguson, George; Lloyd, Brian R.; Puddephatt, Richard J., Organometallics, 1986, vol. 5, # 2, p. 344 - 348

  摘要：

  DOI：
• 作为产物：
  描述：

  dichloro(bis(diphenylphosphino)methane)platinum(II) 、 silver trifluoroacetate 以 二氯甲烷 为溶剂， 以56%的产率得到diphenylphosphanylmethyl(diphenyl)phosphane;platinum(2+);2,2,2-trifluoroacetate
  参考文献：
  名称：

  Bis(carboxylato) complexes of platinum(II). Structural and bonding analysis of [Pt(O₂CR)₂(L–L)][L–L = 2PPh₃, Ph₂PCH₂PPh₂or Fe(C₅H₄PPh₂)₂; R = Me, CF₃, Prⁱor Ph]

  摘要：

  Treatment of [PtCl2(L-L)] [L-L = 2 PPh(3), Ph(2)PCH(2)PPh(2)(dppm) or Fe(C(5)H(4)PPh(2))(2)(dppf)] with Ag(O(2)CR) (R = Me, CF3, Pr-i or Ph) at room temperature generally gave [Pt(O(2)CR)(2)(L-L)] in moderate to good yields. The crystal and molecular structures of [Pt(O(2)CMe)(2)(dppf)]. H2O, [Pt(O(2)CPh)(2)(dppf)]. CH2Cl2 and [Pt(O2CCF3)(2)(dppm)] have been determined by single-crystal X-ray diffractometry. All these complexes show a mononuclear square-planar structure with a chelating diphosphine and two neighbouring (cis) carboxylates in a monodentate mode. These structures contrast those of the parent [Pt-4(mu-O(2)CMe)(8)] and its derivative [Pt-4(en)(4)(mu-O(2)CMe)(4)](4+) (en = ethylenediamine) which are tetrameric, based on octahedral Pt-II, and contain bridging acetates and direct Pt-Pt bonds. Fenske-Hall molecular orbital calculations of these structures confirmed the existence of Pt-Pt bonding interactions. The presence of hard and electronegative ligands like en and acetate incurs a deficiency in sigma-electron density, compared to virtually filled non-bonding orbitals; the former is alleviated by Pt-Pt bonding. d(8) Complexes with ligands like phosphines possessing both sigma-donating and pi-accepting qualities appear to favour the usual square-planar geometry.

  DOI：

  10.1039/dt9960002207

文献信息

• Lloyd, Brian R.; Manojlovic-Muir, Ljubica; Muir, Kenneth W., Organometallics, 1993, vol. 12, # 4, p. 1231 - 1237
  作者：Lloyd, Brian R.、Manojlovic-Muir, Ljubica、Muir, Kenneth W.、Puddephatt, Richard J.

  DOI：——

  日期：——
• Synthesis, structure, and properties of a tetranuclear platinum cluster cation
  作者：Graeme Douglas、Ljubica Manojlovic-Muir、Kenneth W. Muir、Michael C. Jennings、Brian R. Lloyd、Mehdi Rashidi、Guy Schoettel、Richard J. Puddephatt

  DOI：10.1021/om00057a026

  日期：1991.11

  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)3dppm-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.