Ph2PCH2CH2PPh(C5F4N-4) | 528584-60-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: Ph2PCH2CH2PPh(C5F4N-4)
• CAS: 528584-60-3
• 化学式: C₂₅H₁₉F₄NP₂
• 分子量: 471.374
• InChiKey: JKGIJPDRRAORMD-YTTGMZPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  32.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  12.89
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 Ph2PCH2CH2PPh(C5F4N-4) 以 氘代苯 为溶剂， 生成 [((C5Me5)RhCl2)2(μκP,κP-Ph2PCH2CH2PPh(C5F4N-4))]
  参考文献：
  名称：

  Intramolecular Dehydrofluorinative Coupling of the Asymmetric Diphosphine Ph₂PCH₂CH₂PPh(C₅F₄N-4) and Pentamethylcyclopentadienyl Ligands in a Rhodium Complex

  摘要：

  The tetrafluoropyridyl-substituted diphosphine Ph2PCH2CH2PPh(C5F4N-4) (1) has been prepared in three steps from dppe. Comparison of the spectroscopic properties between trans-[RhCl(CO){PPh2(C5F4N-4)}(2)] and analogous complexes of other fluorinated triaryl phosphines reveals the lower basicity of tetrafluoropyridylphosphines relative to pentafluorophenylphosphines. The reaction between [Cp*RhCl(mu-Cl)](2) and 1 in the presence of [BF4-] yielded racemic diastereoisomers of [CP*RhCl(1)] [BF4]. In the SRhRP and RRhSP pair of enantiomers the Cp* and tetrafluoropyridyl groups have a cis disposition about the Rh-P bond, and in the SRhSP and RRhRP pair the groups are trans. In situ NMR experiments reveal that the cis pair, in which the Cp* and tetrafluoropyridyl groups are close, underwent rapid dehydrofluorinative C-C coupling to give the respective enantiomers of [{eta(5),kappaP,kappap-C5Me4CH2-2-C5F3N-4-PPhCH2-CH2PPh2}RhCl] [BF4] (6.[BF4]. The trans pair did not undergo coupling, but isomerized to the cis pair on heating in ethanol. The reaction between [Cp*RhCl(mu-Cl)](2) and 1 in refluxing benzene afforded 6.[BF4] in 64% yield after anion metathesis. The structures of OPPh2-(C5F4N-4), the cis isomer of [Cp*RhCl(1)][BF4], and one enantiomer of 6.[BF4], which crystallizes as a conglomerate, have been determined by single-crystal X-ray diffraction.

  DOI：

  10.1021/om020874p