[N(C₂H₅)₄][Ni(triphenylphosphine)Cl₃] | 20057-56-1

• 英文名称: [N(C₂H₅)₄][Ni(triphenylphosphine)Cl₃]
• 英文别名: [N(C₂H₅)₄][Ni(PPh₃)Cl₃]；[NEt₄][Ni(PPh₃)Cl₃]；[NEt4][NiCl3(PPh3)]
• CAS: 20057-56-1
• 化学式: C₈H₂₀N*C₁₈H₁₅Cl₃NiP
• 分子量: 557.593
• InChiKey: PGKZGEHLPUUAQO-UHFFFAOYSA-K

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：

  [N(C₂H₅)₄][Ni(triphenylphosphine)Cl₃] 、 1,3-双(2,6-二异丙基苯基)咪唑-2-烯 以 四氢呋喃 为溶剂， 反应 0.5h， 以82%的产率得到Ni(PPh₃)(1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)Cl₂
  参考文献：
  名称：

  Mixed NHC/Phosphine Ni(II) Complexes: Synthesis and Their Applications as Versatile Catalysts for Selective Cross-Couplings of ArMgX with Aryl Chlorides, Fluorides, and Methyl Ethers

  摘要：

  New methods for the preparation of mixed NHC/phosphine Ni(II) complexes have been developed. It was shown that the quaternary ammonium cation in the easily available Ni(II) complexes [NEt4] [Ni(PPh3)X-3] (X = Cl and Br) can act as a good leaving group in reactions of [NEt4][Ni(PPh3)X-3] with the bulky ItBu (ItBu = 1,3-ditertbutylimidazol-2-ylidene) or IPr [IPr = 1,3-bis (2,6-diisopropylphenyl)imidazol-2-ylidene] ligarid, resulting in the corresponding mixed NHC/PPh3 Ni(II) complexes Ni(PPh3)-(ItBu)X-2 (X = Cl, 1; X = Br, 2) or Ni(PPh3)(IPr)Br-2 (3) in high yields. The PPh3 ligand in these obtained mixed NHC/PPh3 Ni(II) complexes can be easily substituted by a more electron-donating phosphine ligand, i.e., PC)T, resulting in the corresponding mixed NHC/PCy3 Ni(II) complexes Ni(PCy3)(ItBu)Br-2 (4) and Ni(PCy3)(IPr)Br-2 (5) in high yields. The crystal structures of these NO) complexes have been characterized, which revealed a trans disposition of the NHC ligand to the phosphine ligand. The catalytic behaviors of them on varying the carbene ligand (ItBu vs IPr) as well as the phosphine ligand (PPh3 vs PCy3) were investigated in the cross-coupling of aryl Grignard reagents with a wide range of electrophiles. In addition to a significant synergic effect on their catalytic activities, high selectivity for the activation and transformation of C-Cl, C-F and C-O bonds was achieved based on the rational structural design. Complex 2 showed the highest catalytic activity for the cross, coupling of aryl chlorides and fluorides with aryl Grignard reagents, but exhibit little activity for the cross-coupling of aryl methyl ethers with aryl Grignard reagents. On contrast, complex 4 showed great potential for the aryl methyl ethers involved cross-coupling reactions, although its reactivity for the activation of the C-X bond is very poor. The difference in catalytic activity between 2 and 4 has been successfully employed to construct oligoarenes by selective cross-coupling reactions.

  DOI：

  10.1021/acs.organomet.5b00874
• 作为产物：
  描述：

  bis(triphenylphosphine)nickel(II) chloride 、 以 乙腈 为溶剂， 以56%的产率得到[Ni(Fe(N(CH2CH2S)3)(CO)-S,S')2]
  参考文献：
  名称：

  靶向具有重要催化作用的镍酶金属硫活性位点的合成类似物

  摘要：

  含镍的酶NiFe氢化酶，一氧化碳脱氢酶和乙酰辅酶A合酶能够催化环境方面以及潜在的工业上重要的反应：氢的吸收；二氧化碳/一氧化碳相互转化；并结合一氧化碳以形成乙酰辅酶A。描述了具有与这些酶的活性位点相关的结构特征的镍铁配合物的合成进展，以及第一个甲基化镍铁双金属配合物[{Fe（N S 3）（NO）-S } Ni（CH 3）（dppe）]（N S 3 = N（CH 2 CH 2 S）3 3−），与乙酰辅酶A合酶机制中拟议的机制中间体有关。

  DOI：

  10.1039/b307175h

文献信息

• 含三环己基膦的单膦单氮杂环卡宾镍(II)配合 物及其应用
  申请人：苏州大学

  公开号：CN104098607B

  公开（公告）日：2016-04-20

  本发明公开了一种含三环己基膦的单膦单氮杂环卡宾镍(II)配合物及其应用，所述含三环己基膦的单膦单氮杂环卡宾镍(II)配合物的分子式为(PCy3)Ni[(RNCHCHNR)C]X2，式中，PCy3为三环己基膦；R为叔丁基、2,6-二异丙基苯基或均三甲基苯基；X为氯或溴。本发明中的含三环己基膦的单膦单氮杂环卡宾镍(II)配合物，制备简单易操作，产物易提纯、得率高，且在空气中也可稳定存在。这类单膦单氮杂环卡宾镍(II)配合物可以在温和条件下高效催化芳甲醚和芳基格氏试剂的交叉偶联反应。