(PEt3)2Ni(η2-phenanthrene) | 1094064-25-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (PEt3)2Ni(η2-phenanthrene)
• 英文别名: nickel;phenanthrene;triethylphosphane
• CAS: 1094064-25-1
• 化学式: C₂₆H₄₀NiP₂
• 分子量: 473.241
• InChiKey: DYTYSGSYVBYCHP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.05
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  五氟吡啶 、 (PEt3)2Ni(η2-phenanthrene) 以 氘代甲苯 为溶剂， 生成 trans-[Ni(F)(2-C5NF4)(PEt3)2]
  参考文献：
  名称：

  Experimental Study of the Reaction of a Ni(PEt₃)₂Synthon with Polyfluorinated Pyridines: Concerted, Phosphine-Assisted, or Radical C–F Bond Activation Mechanisms?

  摘要：

  The mechanisms of the C F activation reactions of 2,3,5,6-tetrafluoropyridine and pentafluoropyridine with the phenanthrene adduct (PEt3)(2)Ni(eta(2)-C14H10) and Ni(PEt3)(4) as sources of (PEt3)(2)Ni were investigated. The activation of 2,3,5,6-tetrafluoropyridine proceeds via the mononuclear adduct (PEt3)(2)Ni(eta(2)-2,3,5,6-C5F4HN) (3) in equilibrium with the CH activation product, trans-(PEt3)(2)NiH(2,3,5,6-C5F4N) (2). The C-F activation reaction occurs by concerted oxidative addition, as judged by the observation of cis-(PEt3)(2)NiF(3,5,6-C5F3HN) (4), as an intermediate to trans-(PEt3)(2)NiF(3,5,6-C5F3HN) (1). The dinudear adduct [(PEt3)(2)Ni](2)(mu-eta(2):eta(2)-2,3,5,6-C5F4HN) (5) was not observed. Pentafluoropyridine reacted with the phenanthrene adduct (PEt3)(2)Ni(eta(2)-C14H10) to provide the mononuclear adduct (PEt3)(2)Ni(eta(2)-C5F5N) (6) and the dinuclear adduct [(PEt3)(2)Ni](2)-(mu-eta(2):eta(2)-C5F5N) (11). A (PEt3)(2)Ni adduct of the C-F activation product, (PEt3)(2)Ni[eta(2)-3,4,5,6-C5F4N-2-NiF(PEt3)(2)] (10), and the double C F activation product [trans-(PEt3)(2)NiF](2)(3,4,5-C5F3N) (9) were also assigned by NMR spectroscopy. Complex 10 was a precursor to both trans-(PEt3)(2)NiF(3,4,5,6-C5F4N) (7) and 9. The rate of formation of trans-(PEt3)(2)NiF(3,4,5,6-C5F4N) (7) is not first order with respect to the concentration of 6. The EPR spectrum of (PEt3)(2)Ni(eta(2)-C14H10) and pentafluoropyridine, in a toluene solution that was frozen in N-2(1) during reaction at -40 degrees C, revealed signals consistent with the speculative formulation (PEt3)(2)Ni(2-C5F4N). These results suggest that pathways other than concerted oxidative addition or phosphine-assisted pathways arising from 6 are required to account for the unusual selectivity of the C F activation of pentafluoropyridine by the (PEt3)(2)Ni fragment.

  DOI：

  10.1021/om200990g
• 作为产物：
  描述：

  菲 、 bis(triethylphosphine)nickel(II) bromide 在 sodium 作用下， 生成 (PEt3)2Ni(η2-phenanthrene)
  参考文献：
  名称：

  用双（三乙基膦）镍合成子对四氟苯进行 C-F 键活化的意外中间体和产物：Ni(0) 快速可逆 C-H 键活化的直接证据

  摘要：

  (PEt(3))(2)Ni(eta(2)-C(14)H(10)) 的反应，反应性 Ni(PEt(3))(2) 部分的来源，与 1,2 ,4,5-F(4)C(6)H(2) 产生三种 CF 键活化产物的混合物，其中包括意想不到的产物 (PEt(3))(2)NiF-2,3,5,6- F(4)C(6)H 和 (PEt(3))(2)NiF-2,3,5-F(3)C(6)H(2)。通过 (19)F 和 (1)H NMR 监测反应混合物还揭示了 CH 键活化产物 (PEt(3))(2)NiH-2,3,5,6-F(4)C 的存在(6) H 在快速平衡反应中产生。这一观察结果提供了对修饰镍配合物以在各种多氟化芳烃底物中选择性 CF 键活化所需的步骤的深入了解，但也扩展了简单镍化合物在 CH 键活化和功能化反应中的潜力。

  DOI：

  10.1021/ja8081395