2-[(diphenylphosphino)methyl]pyridinenickel dichloride | 1005390-59-9

• 英文名称: 2-[(diphenylphosphino)methyl]pyridinenickel dichloride
• 英文别名: [Ni(2-((diphenylphosphino)methyl)pyridine)Cl2]
• CAS: 1005390-59-9
• 化学式: C₁₈H₁₆Cl₂NNiP
• 分子量: 406.902
• InChiKey: LITFBJBXUORTPI-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  氯化镍二甲氧基乙烷 、 二苯基(吡啶-2-基甲基)膦 以 二氯甲烷 为溶剂， 以87%的产率得到2-[(diphenylphosphino)methyl]pyridinenickel dichloride
  参考文献：
  名称：

  吡啶膦配体的镍和钯配合物作为乙烯低聚催化剂

  摘要：

  吡啶膦配体1 - 5已被用来制备中性二氯化镍配合物，中性methylpalladium氯配合物，和阳离子methylpalladium络合物。配体由二苯基膦和吡啶部分组成，并且在连接那些供体基团的主链上不同。镍配合物9 - 13是顺磁性配合物，并对其进行了表征通过元素分析，高分辨率质谱，而且，对于10和12，单晶X射线衍射。中性钯配合14 - 18进行了充分的特点。对络合物15进行单晶X射线衍射和16，以及可变温度NMR证明16显示出金属环的缓慢转化。阳离子钯物种19 - 23从氯化物抽象后的中性配合物获得。像其中性前体一样，21显示出缓慢的环反转。用MAO活化后，将镍物质评估为乙烯低聚催化剂。所有配合物均具有高活性，TOF在24×10 3和85×10 3之间（mol C 2 H 4）·（mol Ni·h）-1。在所有情况下，丁烯都是主要产物，占产物的76至96 mol％。1-丁烯的选择性

  DOI：

  10.1021/om800903n

文献信息

• Mono- and Dinuclear Nickel Complexes with Phosphino-, Phosphinito-, and Phosphonitopyridine Ligands: Synthesis, Structures, and Catalytic Oligomerization of Ethylene
  作者：Anthony Kermagoret、Pierre Braunstein

  DOI：10.1021/om7008759

  日期：2008.1.1

  The P,N-type ligands 2-[(diphenylphosphino)methyllpyridine (12), 2-[2-(diphenylphosphino)ethyl]pyridine (13), 2-methyloxy(diphenylphosphino)pyridine (14), 2-methyloxy(dibenzyl-1,2-oxaphosphorino)pyridine (15), and 2-methyloxy(di-tert-butylphosphino)pyridine (16) have been prepared in good yields, and 12 and 13 have been used to synthesize Ni(II) complexes of formula [Ni(P,N)Cl-2], 17 (P,N = 12) and 18 (P,N = 13), by reaction with NiCl2 in methanol. The crystal structure of 18 has been determined by X-ray diffraction to be dinuclear with a distorted square-base pyramidal geometry around the Ni(II) centers. To examine the possible influence of the nature of the spacer link between the P and N donor atoms, we compared ligand 13, with a CH2CH2,, spacer, with 14 and 16, which have a isosteric CH2-O spacer. Reactions of the phosphinitopyridine ligands 14 and 16 and of the phosphonitopyridine 15 with [NiX2(DME)] (X = Cl or Br) afforded the complexes [Ni(P,N)Cl-2] 20 (X = Cl; P,N = 14), 21 (X = Br; P,N = 14), 22 (X = Cl; P,N = 16), and 23 (X = Cl; P,N = 15), respectively. The mononuclear structure of complex 22 has been established by X-ray diffraction and showed a distorted tetrahedral geometry around the metal center. Complexes 17, 18, and 20-22 have been tested as precatalysts in the oligornerization of ethylene, with AlEtCl2 or MAO as cocatalyst, in order to evaluate the influence of the stereoelectronic properties of the phosphorus substituents. With only 6 equiv of AlEtCl2, as cocatalyst and 4 x 10(-5) Mol precatalyst, complex 18 was the most active, with turnover frequencies (TOF) up to 91 200 C2H4/(mol Ni center dot h), and 20 with 2 equiv of AlEtCl2 showed the highest selectivities for ethylene dimers (up to 97%) and in 1-butene (up to 72%). When only 10(-5) mol precatalyst was used, the TOF values went up to 207 600 for 18 and 150 100 for 20. With only 25 equiv of MAO as cocatalyst, complex 18 was again the most active, with TOF values up to 20 600 C2H4/(mol Ni center dot h). Despite the high selectivity for C-4 olefins of 17, 18, 20, and 21 (up to 93% for 20), 22 presented the best selectivities for 1-butene (up to 73%) with MAO as cocatalyst, and its high reactivity for the reinsertion of 1-butene resulted in 2-ethyl-1-butene being the main product of the catalytic reaction (up to 91%).