[(1,2-bis(di-tert-butylphosphino)ethane)NiI] | 1438463-44-5

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [(1,2-bis(di-tert-butylphosphino)ethane)NiI]
• 英文别名: [(dtbpe)NiI]
• CAS: 1438463-44-5
• 化学式: C₁₈H₄₀INiP₂
• 分子量: 504.058
• InChiKey: IXGQYERJHHLMLQ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.15
• 重原子数：
  22.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  [(1,2-bis(di-tert-butylphosphino)ethane)Ni(CH2CH2COO)] 在 caesium carbonate 作用下， 以 氘代四氢呋喃 、 二氯甲烷-D2 为溶剂， 反应 2.5h， 生成 [(1,2-bis(di-tert-butylphosphino)ethane)NiI]
  参考文献：
  名称：

  Mechanistic Details of the Nickel-Mediated Formation of Acrylates from CO₂, Ethylene and Methyl Iodide

  摘要：

  Methyl iodide induces the stoichiometric cleavage of nickelalactones, which are key intermediates in the nickel-mediated reaction of CO2 and alkenes to acrylates. Herein, we propose a modified and extended mechanism for this reaction on the basis of theoretical and experimental investigations for the bidentate P ligand 1,2-bis(di-tert-butylphosphino)ethane (dtbpe). The calculated elementary steps agree well with experimental findings: reaction barriers are reasonable and explain the facile liberation of acrylate from a nickelalactone by methyl iodide. We were able to isolate reactive intermediates and to verify the existence of proposed reaction pathways. Additionally, we have identified unproductive pathways leading to byproducts (e.g., propionates and catalytically inactive organometallic species). Although those side reactions can be suppressed to a certain extent, the strong binding of acrylate to nickel prevents a catalytic reaction, at least for the chosen ligand.

  DOI：

  10.1021/om400262b