dichlorobis[(+/-)-benzylcyclohexylphenylphosphine]nickel(II) | 244070-86-8

• 英文名称: dichlorobis[(+/-)-benzylcyclohexylphenylphosphine]nickel(II)
• CAS: 244070-86-8
• 化学式: C₃₈H₄₆Cl₂NiP₂
• 分子量: 694.327
• InChiKey: KWPSJBWKOPHBFK-FFYRYUNVSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Pd(DL-α-methylbenzylamine)(μ-Cl)]₂ 、 dichlorobis[(+/-)-benzylcyclohexylphenylphosphine]nickel(II) 以 四氢呋喃 为溶剂， 生成 (C6H4CH(CH3)(NH2))PdCl(benzylcyclohexylphenylphosphine)
  参考文献：
  名称：

  Resolution of Benzylcyclohexylphenylphosphine by Palladium(II)−Amine Metallacycles. A New Ligand for Asymmetric Hydrovinylation

  摘要：

  The synthesis of benzylcyclohexylphenylphosphine and its resolution by means of optically active palladium metallacycles are reported. The absolute configuration of (R-C,S-P)-[PdCl(C6H4CHMeNMe2)(PBzCyPh)] has been determined by single-crystal X-ray analyses. The allyl complex [Pd(eta(3)-2-MeC3H4)(PBzCyPh)S]BF4, prepared in situ from [Pd(eta(3)-2-MeC3H4)Cl(PBzCyPh)] and AgBF4 in CH2Cl2 solution, was used as a precatalyst for asymmetric hydrovinylatiom of styrene and 2-vinylnaphthalene. This system permits the synthesis of 3-phenyl-1-butene and 3-(2-naphthyl)-1-butene with good ee values working in very mild conditions of temperature (15 degrees C).

  DOI：

  10.1021/om990302d
• 作为产物：
  描述：

  benzylcyclohexylphenylphosphine 、 nickel dichloride 以 四氢呋喃 、 乙醇 为溶剂， 以60%的产率得到dichlorobis[(+/-)-benzylcyclohexylphenylphosphine]nickel(II)
  参考文献：
  名称：

  Resolution of Benzylcyclohexylphenylphosphine by Palladium(II)−Amine Metallacycles. A New Ligand for Asymmetric Hydrovinylation

  摘要：

  The synthesis of benzylcyclohexylphenylphosphine and its resolution by means of optically active palladium metallacycles are reported. The absolute configuration of (R-C,S-P)-[PdCl(C6H4CHMeNMe2)(PBzCyPh)] has been determined by single-crystal X-ray analyses. The allyl complex [Pd(eta(3)-2-MeC3H4)(PBzCyPh)S]BF4, prepared in situ from [Pd(eta(3)-2-MeC3H4)Cl(PBzCyPh)] and AgBF4 in CH2Cl2 solution, was used as a precatalyst for asymmetric hydrovinylatiom of styrene and 2-vinylnaphthalene. This system permits the synthesis of 3-phenyl-1-butene and 3-(2-naphthyl)-1-butene with good ee values working in very mild conditions of temperature (15 degrees C).

  DOI：

  10.1021/om990302d

文献信息

• Optically active cyclopalladated compounds containing P-chiral ligands. Restricted rotation around the PdP bond
  作者：Joan Albert、Ramón Bosque、J Magali Cadena、Sergio Delgado、Jaume Granell

  DOI：10.1016/s0022-328x(01)01111-1

  日期：2001.9

  bond and the conformation of the Pd–phosphine fragment can be found and NMR data permit the assignment of the absolute configuration of the phosphine in [PdCl(C10H6CHMeNMe2)(PBnCyPh)]. Several molecular mechanics geometry optimizations were performed using the MMFF94 force field to estimate the height of the energy barrier corresponding to the rotation of the phosphine ligands around the PdP bond. These

  报道了旋光络合物[PdCl（C 10 H 6 CHMeNMe 2）L]（L ＝ PPh 3，PBn 2 Ph，PHBnPh和PBnCyPh）的合成和仲膦PHBnPh的拆分。这些单核化合物的NMR数据研究表明，在某些配合物中，绕Pd = P键的旋转受到限制。可以发现与PdC键相邻的芳族质子的δ值与Pd-膦片段的构象之间的关系，并且NMR数据可以确定[PdCl（C 10 H 6）中膦的绝对构型化学2）（PBnCyPh）]。使用MMFF94力场进行了一些分子力学几何优化，以估计与PdP键周围的膦配体旋转对应的能垒高度。这些计算表明，如果该膦含有至少一个苄基，则绕Pd = P键的旋转受到限制，并且与通过一维和二维NMR在溶液中获得的结果一致。