Ni(PPh3)3BF4 | 230950-98-8

• 英文名称: Ni(PPh3)3BF4
• 英文别名: Ni(PPh₃)₃BF₄
• CAS: 230950-98-8
• 化学式: BF₄*C₅₄H₄₅NiP₃
• 分子量: 932.367
• InChiKey: CYDOVVRSCSTNQE-UHFFFAOYSA-N

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：

  Ni(PPh3)3BF4 、 亚磷酸三乙酯 以 氘代氯仿 为溶剂， 生成
  参考文献：
  名称：

  摘要：

  The reactions of the individual cationic complex [(PPh3)(3)Ni]BF4 with unsaturated hydrocarbons (ethene, propene, and styrene), as well as the reaction of the sigma -alkyl Ni(I) complex (PPh3)(2)Ni-CH(COOC2H5)(2) (obtained in situ) with ethene, were studied using EPR, UV, and NMR spectroscopy. It was found that stable dimeric carbocationic sigma -alkyl Ni(I) complexes are intermediates in the reactions of unsaturated hydrocarbons with cationic Ni(I) complexes. The transformations of unsaturated hydrocarbons on cationic Ni(I) complexes were explained in terms of an experimentally justified ionic coordination mechanism. A stable mononuclear Ni(I) complex with a Ni-C sigma -bond was synthesized and characterized using EPR. An organonickel(I) complex with pi- and sigma -bonded carbon atoms was identified using EPR and NMR methods.

  DOI：

  10.1023/a:1012509802979
• 作为产物：
  描述：

  四(三苯基膦)镍 、 trifluoroborane diethyl ether 以 甲苯 为溶剂， 以75%的产率得到Ni(PPh3)3BF4
  参考文献：
  名称：

  一价镍的阳离子配合物作为苯乙烯聚合催化剂

  摘要：

  通过EPR和13 C NMR光谱研究了[Ni（PPh 3）3 ] BF 4与苯乙烯的相互作用以及苯乙烯在聚合反应中的转化产物。苯乙烯与[Ni（PPh 3）3 ] BF 4相互作用形成的Ni（I）σ-碳配位化合物的结构Ni（I）的阳离子膦络合物的详细特征。发现苯乙烯聚合反应在σ-碳酸盐配合物的配位中心的参与下发生（配位催化），而端粒化反应在该配合物的阳离子中心的参与下发生（离子催化）。所得的聚合物含有活性末端双键。它是用于合成接枝共聚物的大分子单体。所发现的醇对增长的聚合物链进行亲核加成的能力为制备功能性聚合物和嵌段共聚物提供了强大的可能性。

  DOI：

  10.1007/s10975-005-0126-4

文献信息

• ——
  作者：P. B. Kraikivskii

  DOI：10.1023/a:1024042429252

  日期：——

  Reactions of aluminium tribromide with the Ni(0) phosphine and phosphite complexes are studied by EPR method. AlBr3 was found to cause the oxidation of the transition metal in the (PPh3)(4)Ni complex to the univalent state with the formation of the tetracoordinated (PPh3)(3)NiBr complex. With an excess of AlBr3, the phosphine ligands are eliminated from the coordination sphere of Ni(I), and the coordinatively unsaturated complexes are destroyed to give the colloidal nickel. In the reaction of (P(OEt)(3))(4)Ni with AlBr3, Ni(0) is also oxidized to Ni(I), but the acido ligand is not eliminated even with a 15-fold excess of the Lewis acid. The activity of catalytic systems on the basis of the Ni(0)phosphine complexes and the Lewis acids in the low-molecular oligmerization reactions of olefines is determined by the cationic coordinatively unsaturated Ni(I) complexes formed in these systems.
• Saraev; Kraikivskii; Zaitsev, Russian Journal of Coordination Chemistry, 2000, vol. 26, # 7, p. 487 - 491
  作者：Saraev、Kraikivskii、Zaitsev、Tkach、Schmidt

  DOI：——

  日期：——
• Influence of alcohols on the formation of the nickel complexes active in ethene oligomerization in the catalytic system Ni(PPh3)4/BF3·OEt2
  作者：V.V. Saraev、P.B. Kraikivskii、S.N. Zelinskiy、D.A. Matveev、A.I. Vilms、A.V. Rohin、K. Lammertsma

  DOI：10.1016/j.molcata.2005.04.036

  日期：2005.7

  The influence of ethanol and selected other alcohols on the formation of active nickel complexes for ethylene oligomerization was studied for the Ni(PPh3)(4)BF(3)center dot OEt2 system by EPR and H-1 NMR spectroscopy. Both the presence of Ni(I) complexes and Ni(II) hydrides could be established. Coordinatively unsaturated Ni(I) complexes were shown to be the active catalysts for ethylene oligomerization, whereas the Ni(II) hydrides were shown to be inactive. The alcohol act as a promoter for the Ni(PPh3)(4)BF(3)center dot OEt2 by facilitating the formation of the active Ni(I) complexes. (c) 2005 Elsevier B.V. All rights reserved.