rac-2-[1'-(diphenylphosphanyl)ethyl]-4,4-dimethyl-4,5-dihydrooxazole | 708276-78-2

• 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: rac-2-[1'-(diphenylphosphanyl)ethyl]-4,4-dimethyl-4,5-dihydrooxazole
• 英文别名: [(1S)-1-(4,4-dimethyl-5H-1,3-oxazol-2-yl)ethyl]-diphenylphosphane
• CAS: 708276-78-2
• 化学式: C₁₉H₂₂NOP
• 分子量: 311.364
• InChiKey: LHVAGKFUWSBHOE-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  氯化镍二甲氧基乙烷 、 rac-2-[1'-(diphenylphosphanyl)ethyl]-4,4-dimethyl-4,5-dihydrooxazole 以 二氯甲烷 为溶剂， 以90%的产率得到[Ni(μ-Cl)Cl(2-[1'-(diphenylphosphanyl)ethyl]-4,4-dimethyl-4,5-dihydrooxazole)]2
  参考文献：
  名称：

  Nickel Complexes with Oxazoline-Based P,N-Chelate Ligands:  Synthesis, Structures, and Catalytic Ethylene Oligomerization Behavior

  摘要：

  The phosphinooxazoline ligands 9-12 have been prepared and used to examine and compare the catalytic properties of their corresponding Ni(II) complexes in ethylene oligomerization. The molecular structure of rac-2-[1'-(diphenylphosphanyl)ethyl]-4,4-dimethyl-4,5-dihydrooxazole (10) has been determined by X-ray diffraction. The paramagnetic Ni(II) complexes [NiX(mu-X)(P,N)](2) (19, X = Br, P,N = 2-[(diphenylphosphanyl)methyl]-4,4-dimethyl-4,5-dihydrooxazole (9)); 20, X = Cl, P,N = 9; 21, X = Cl, P,N = 10; 22, X Cl; P,N = 2-[(diphenylphosphanyl)methyl]-4-(R)-phenyl-4,5-dihydrooxazole (12); 23, X = Br, P,N = 12) and [NiCl2(P,N)] (24; P,N = 2-[1'-(diphenylphosphanyl)-1'-methylethyl]-4,4-dimethyl-4,5-dihydrooxazole (11) were prepared in yields of 79-90%, and 19 and 24 have been characterized by X-ray diffraction. The former is a dinuclear complex with distorted-trigonal-bipyramidal geometry around the Ni(II) centers, whereas 24 is a mononuclear, tetrahedral complex, which underlines the strong influence of a substituent on the carbon atom a to P. The metal coordination sphere in complexes 19-24 was determined in solution by the Evans method to be trigonal bipyramidal for 19-23 and tetrahedral for 24. Whereas complexes 19-23 and [NiCl2(PCy3)(2)] were inactive for ethylene polymerization in the presence of methylaluminoxane (MAO), the mononuclear complex 24 gave a TOF of 7900 mol of C2H4/((mol of Ni) h) with a selectivity for 1-butene of 38%. Complexes 19, 20, and 22 were inactive for the oligomerization of ethylene in the presence of NaBH4, but 19, 21, and 24 were active with AlEtCl2 as a cocatalyst. Activities and selectivities were compared to those of [NiCl2-(PCy3)(2)], a typical precatalyst used in the dimerization of alpha-olefins. Complex 19 yielded a turnover frequency of 36 300 mol of C2H4/((mol of Ni) h) in the presence of 14 equiv of AlEtCl2. In the presence of only 6 equiv of cocatalyst, the Ni complexes 21 and 24 showed TOF values of 38 100 and 45 900 mol of C2H4/((mol of Ni) h), respectively, higher than that of 27 200 mol of C2H4/((mol of Ni) h) obtained with [NiCl2(PCy3)(2)].

  DOI：

  10.1021/om034197q

文献信息

• Nickel Complexes with Oxazoline-Based <i>P</i>,<i>N</i>-Chelate Ligands:  Synthesis, Structures, and Catalytic Ethylene Oligomerization Behavior
  作者：Fredy Speiser、Pierre Braunstein、Lucien Saussine、Richard Welter

  DOI：10.1021/om034197q

  日期：2004.5.1

  The phosphinooxazoline ligands 9-12 have been prepared and used to examine and compare the catalytic properties of their corresponding Ni(II) complexes in ethylene oligomerization. The molecular structure of rac-2-[1'-(diphenylphosphanyl)ethyl]-4,4-dimethyl-4,5-dihydrooxazole (10) has been determined by X-ray diffraction. The paramagnetic Ni(II) complexes [NiX(mu-X)(P,N)](2) (19, X = Br, P,N = 2-[(diphenylphosphanyl)methyl]-4,4-dimethyl-4,5-dihydrooxazole (9)); 20, X = Cl, P,N = 9; 21, X = Cl, P,N = 10; 22, X Cl; P,N = 2-[(diphenylphosphanyl)methyl]-4-(R)-phenyl-4,5-dihydrooxazole (12); 23, X = Br, P,N = 12) and [NiCl2(P,N)] (24; P,N = 2-[1'-(diphenylphosphanyl)-1'-methylethyl]-4,4-dimethyl-4,5-dihydrooxazole (11) were prepared in yields of 79-90%, and 19 and 24 have been characterized by X-ray diffraction. The former is a dinuclear complex with distorted-trigonal-bipyramidal geometry around the Ni(II) centers, whereas 24 is a mononuclear, tetrahedral complex, which underlines the strong influence of a substituent on the carbon atom a to P. The metal coordination sphere in complexes 19-24 was determined in solution by the Evans method to be trigonal bipyramidal for 19-23 and tetrahedral for 24. Whereas complexes 19-23 and [NiCl2(PCy3)(2)] were inactive for ethylene polymerization in the presence of methylaluminoxane (MAO), the mononuclear complex 24 gave a TOF of 7900 mol of C2H4/((mol of Ni) h) with a selectivity for 1-butene of 38%. Complexes 19, 20, and 22 were inactive for the oligomerization of ethylene in the presence of NaBH4, but 19, 21, and 24 were active with AlEtCl2 as a cocatalyst. Activities and selectivities were compared to those of [NiCl2-(PCy3)(2)], a typical precatalyst used in the dimerization of alpha-olefins. Complex 19 yielded a turnover frequency of 36 300 mol of C2H4/((mol of Ni) h) in the presence of 14 equiv of AlEtCl2. In the presence of only 6 equiv of cocatalyst, the Ni complexes 21 and 24 showed TOF values of 38 100 and 45 900 mol of C2H4/((mol of Ni) h), respectively, higher than that of 27 200 mol of C2H4/((mol of Ni) h) obtained with [NiCl2(PCy3)(2)].