[(η3:η2-indenyl-(CH2)2CHCH2)Ni(PPh3)][BPh4] | 863017-79-2

• 英文名称: [(η3:η2-indenyl-(CH2)2CHCH2)Ni(PPh3)][BPh4]
• CAS: 863017-79-2
• 化学式: C₂₄H₂₀B*C₃₁H₂₈NiP
• 分子量: 809.461
• InChiKey: XHUOOQLJBITRQV-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：

  [(η3:η2-indenyl-(CH2)2CHCH2)Ni(PPh3)][BPh4] 以 not given 为溶剂， 生成 [(η3:η0-indenyl-(CH2)2CHCH2)Ni(PPh3)2][BPh4]
  参考文献：
  名称：

  Indenyl-Nickel Complexes Bearing a Pendant, Hemilabile Olefin Ligand:  Preparation, Characterization, and Catalytic Activities

  摘要：

  The reaction of (PPh3)(2)NiCl2 with Li[Ind boolean AND CH=CH2] gave the neutral complexes (eta:eta(0)-Ind boolean AND CH=CH2)Ni(PPh3)Cl (Ind = indenyl; boolean AND = (CH2)(2), 1a; Si(Me)(2)CH2, 1b), which were subjected to Cl- abstraction to give the corresponding cationic complexes [(eta:eta(2)-Ind boolean AND CH= CH2)Ni(PPh3)](+) (boolean AND = (CH2)(2), 2a; Si(Me)(2)CH2, 2b). The bis(phosphine) derivatives [(eta:eta(0)-Ind-CH2CH2CH=CH2)Ni(PPh3)(2)](+) (3a) and [(eta(3)-allyl)Ni(PPh3)(2)](+) (4) formed gradually from room-temperature solutions of 2a and 2b, respectively, even in the absence of added PPh3. On the other hand, [(eta:eta(0)-Ind-SiMe2CH2CH=CH2)Ni(PPh3)(2)](+) (3b) was detected only when PPh3 was added to a CD2Cl2 solution of 2b. The lability of the vinyl moiety in 2 allows these complexes to act as single-component precatalysts for the polymerization and hydrosilylation of styrene; the latter reaction requires little or no induction period with the hydrosilanes PhRSiH2 (R= Ph, Me, H) and proceeds with up to 1000 catalytic turnovers. Compounds 1a, 1b, 2a, 3a, and 4 have been characterized by NMR and single-crystal X-ray diffraction studies, whereas 2b and 3b were identified by NMR spectroscopy. Structural information gleaned from both solid-state and solution data provide important information on the Ni-olefin bonding in 2a and 2b and indicate that the Ni-Ind interactions in these complexes are affected by the significant trans influence of the chelating olefin moiety.

  DOI：

  10.1021/om050285u
• 作为产物：
  描述：

  (η3:η0-indenyl-(CH2)2CHCH2)Ni(PPh3)Cl 、 四苯硼钠 以 二氯甲烷 为溶剂， 以45%的产率得到[(η3:η2-indenyl-(CH2)2CHCH2)Ni(PPh3)][BPh4]
  参考文献：
  名称：

  Indenyl-Nickel Complexes Bearing a Pendant, Hemilabile Olefin Ligand:  Preparation, Characterization, and Catalytic Activities

  摘要：

  The reaction of (PPh3)(2)NiCl2 with Li[Ind boolean AND CH=CH2] gave the neutral complexes (eta:eta(0)-Ind boolean AND CH=CH2)Ni(PPh3)Cl (Ind = indenyl; boolean AND = (CH2)(2), 1a; Si(Me)(2)CH2, 1b), which were subjected to Cl- abstraction to give the corresponding cationic complexes [(eta:eta(2)-Ind boolean AND CH= CH2)Ni(PPh3)](+) (boolean AND = (CH2)(2), 2a; Si(Me)(2)CH2, 2b). The bis(phosphine) derivatives [(eta:eta(0)-Ind-CH2CH2CH=CH2)Ni(PPh3)(2)](+) (3a) and [(eta(3)-allyl)Ni(PPh3)(2)](+) (4) formed gradually from room-temperature solutions of 2a and 2b, respectively, even in the absence of added PPh3. On the other hand, [(eta:eta(0)-Ind-SiMe2CH2CH=CH2)Ni(PPh3)(2)](+) (3b) was detected only when PPh3 was added to a CD2Cl2 solution of 2b. The lability of the vinyl moiety in 2 allows these complexes to act as single-component precatalysts for the polymerization and hydrosilylation of styrene; the latter reaction requires little or no induction period with the hydrosilanes PhRSiH2 (R= Ph, Me, H) and proceeds with up to 1000 catalytic turnovers. Compounds 1a, 1b, 2a, 3a, and 4 have been characterized by NMR and single-crystal X-ray diffraction studies, whereas 2b and 3b were identified by NMR spectroscopy. Structural information gleaned from both solid-state and solution data provide important information on the Ni-olefin bonding in 2a and 2b and indicate that the Ni-Ind interactions in these complexes are affected by the significant trans influence of the chelating olefin moiety.

  DOI：

  10.1021/om050285u