{WH2Cl2(Ph2PCH2CH2PPh2)2} | 54766-18-6

• 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: {WH2Cl2(Ph2PCH2CH2PPh2)2}
• CAS: 54766-18-6
• 化学式: C₅₂H₅₀Cl₂P₄W
• 分子量: 1053.62
• InChiKey: CBWLRJDLYANTNA-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  11.35
• 重原子数：
  59.0
• 可旋转键数：
  8.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  盐酸 、 trans-[WH(η(3)-C3H5)(Ph2PCH2CH2PPh2)2] 以 四氢呋喃 为溶剂， 生成 {WH2Cl2(Ph2PCH2CH2PPh2)2}
  参考文献：
  名称：

  Metal hydrides as intermediates in the reactions of coordinated unsaturated hydrocarbons: formation of propyne by protonation of trans- [WH(η3-C5H5) (Ph2PCH2CH2PPh2)2]

  摘要：

  The reaction of anhydrous HCl with trans-[WH(eta(3)-C3H5) (dppe)(2)] (dppe = Ph2PCH2CH2PPh2) in tetrahydrofuran gives [WH2Cl2-(dppe)(2)] together with propene and propyne. Detailed product analyses and kinetic studies demonstrate that propene and propyne are formed by protonation of the allyl residue and the metal, respectively. The most favoured site of protonation is the allyl group to form [WH(eta(2)MeCHCH(2)) (dppe)(2)](+), which releases propene and subsequently forms [WH2Cl2(dppe)(2)]. This is the exclusive hydrocarbon-forming pathway at low concentrations of HCl. The propyne-forming pathway dominates at high concentrations of acid, and involves diprotonation of the metal followed by loss of dihydrogen probably to give the coordinatively-unsaturated species, [WH(eta(3)-C3H5) (dppe)(2)](2+) which rearranges to [WH2(eta(2)-MeCCH) (dppe)(2)](2+), then releases propyne and subsequently forms [WH2Cl2(dppe)2]. The possible mechanisms for the allyl-to-propyne rearrangment are discussed in the light of GLC time-course experiments monitoring the release of the gases. The X-ray crystal structures of IMH(eta(3)-C3H5) (dppe)(2)] (M = Mo or W) show that both complexes have an approximate octahedral geometry about the metal with the hydride group trans to the allyl residue.

  DOI：

  10.1016/s0020-1693(96)05588-0