双(三乙基膦)镍蒽 | 135709-29-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 中文名称: 双(三乙基膦)镍蒽
• 英文名称: bis(triethylphosphine)nickel anthracene
• 英文别名: [Ni(triethylphosphine)2(η2-anthracene)]；[(PPh3)2Ni(η2-anthracene)]；Ni(η2-anthracene)(PEt3)2；anthracene;nickel;triethylphosphane
• CAS: 135709-29-4；143301-25-1
• 化学式: C₂₆H₄₀NiP₂
• 分子量: 473.241
• InChiKey: NHOKTKZGJNZUAM-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：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  双(三乙基膦)镍蒽 以 氘代甲苯 为溶剂， 生成 [Ni(PEt3)2((3,4-η2)-1,2,3,5-tetrafluorobenzene)]
  参考文献：
  名称：

  反应性Ni（PEt 3）2合成子在四氟苯的CF活化中中间体的表征：联合计算和实验研究

  摘要：

  蒽加合物（PET反应3）2的Ni（η 2 -C 14 ħ 10）与1,2,3,4-四氟揭示NMR光谱对直接平衡生产双核加成物的证据[（PET 3）2倪] 2（μ-η 2：η 2 -C 6 ˚F 4 ħ 2）和单核加成物（PET 3）2的Ni（η 2 -C 6 ˚F 4 ħ 2）。同样，（PEt 3）2的反应的Ni（η 2 -C 14 ħ 10）与1,2,4,5-和1,2,3,5-四氟揭示NMR光谱证据为平衡生产双核加合物和单核加合物，也是C-H活化产物（PEt 3）2 NiH（C 6 F 4 H）。加合物和CH活化产物的转化率都太低，无法分离，而且低浓度阻碍了完整的NMR光谱表征。易于制备的（PEt 3）2 NiMe 2与异丁烯的反应可原位产生（PEt 3）2 Ni（η）2 -H 2 C = CMe 2）作为更具反应性的Ni（PEt 3）2合成子。的反应（PET 3）2的Ni（η 2 -H

  DOI：

  10.1021/om100699d
• 作为产物：
  描述：

  bis(triethylphosphine)nickel(II) chloride 、 蒽 在 Mg or C₈K 作用下， 以 not given 为溶剂， 生成 双(三乙基膦)镍蒽
  参考文献：
  名称：

  Synthesis and fluxional behavior of [bis(trialkylphosphine)nickelio]anthracene (alkyl = Et, Bu)

  摘要：

  The title compounds were prepared from the respective (R3P)2NiCl2 complexes and magnesium-anthracene-(THF)3 (or anthracene in the presence of Mg or C8K). The assignment of the anthracene proton NMR signals using NOE in conjunction with magnetization-transfer techniques is described. The complexes undergo haptotropic rearrangements in which the (R3P)2Ni moiety migrates between the two terminal rings of the coordinated anthracene. The rates of these processes are concentration independent and unaffected by the presence of free anthracene and tris(trialkylphosphine)nickel. Kinetic studies in the temperature range -60 to +70-degrees-C using line shape analysis and spin saturation transfer techniques were carried out. It was found that DELTA-H double-ended-dagger = 13.6 kcal mol-1 and DELTA-S double-ended-dagger = -4.3 eu for the haptotropic rearrangement in 2, and similar values were found for 1. Possible mechanisms are discussed. According to H-1, C-13, and P-31 NMR data, the coordination number between the anthracene and the (R3P)2Ni moiety is 4. However, an equilibrium between two eta(2) structures with DELTA-G double-ended-dagger less-than-or-equal-to 4 kcal mol-1 cannot be ruled out.

  DOI：

  10.1021/om00037a054

文献信息

• A one-pot method for the preparation of (R3P)2Ni0L complexes
  作者：Amnon Stanger、Anat Shazar

  DOI：10.1016/0022-328x(93)80480-y

  日期：1993.10

  (R3P)2Ni0L complexes is described. The method is based on the reductive elimination of (R3P)2NiMe2 [which is prepared in situ from the corresponding (R3P)2NiCl2 and MeLi] in the presence of a free ligand. The elimination can be induced thermally (at r.t. or higher) or photochemically. A comparison between the thermal and photochemical methods was made with several phosphine-nickel complexes.

  描述了一种新的通用的一锅法制备（R 3 P）2 Ni 0 L配合物。该方法基于（R 3 P）2 NiMe 2 [由相应的（R 3 P）2 NiCl 2和MeLi原位制备]在游离配体存在下的还原消除。消除可以通过热（在室温或更高温度下）或光化学诱导。用几种膦-镍配合物对热和光化学方法进行了比较。
• Carbon−Hydrogen Bond Oxidative Addition of Partially Fluorinated Aromatics to a Ni(P^<i>i</i>Pr₃)₂Synthon: The Influence of Steric Bulk on the Thermodynamics and Kinetics of C−H Bond Activation
  作者：Jillian A. Hatnean、Robert Beck、Jenna D. Borrelli、Samuel A. Johnson

  DOI：10.1021/om1008499

  日期：2010.11.22

  5- and 1,2,3,4-C6F4H2 afforded analogous compounds, which demonstrates that C−H bond activation is kinetically accessible at room temperature with 1,2,3,4-tetrafluorobenzene despite the presence of a single ortho-fluorine substituent adjacent to the site of activation. The room-temperature reactions of the C−H activation products (PiPr3)2NiH(ArF) (ArF = 2,3,5,6-C6F4H; C6F5) with 3-hexyne provided a

  （P的反应我镨3）2的NiCl 2与蒽加合物（THF）3的Mg（η 2 -C 14 ħ 10）在THF提供的蒽加合物（P我镨3）2的Ni（η 2 -C 14 H 10）。在芳族溶剂（苯，甲苯，均三甲苯）双之间存在热平衡（膦）镍（0）蒽加成物，（P我镨3）2的Ni（η 2 -C 14 ħ 10），以及单膦溶剂加成物，（P我镨3）的Ni（η 6 -溶剂）。的（P反应我镨3）2的Ni（η 2 -C 14 ħ 10）与1,2,4,5--C 6 ˚F 4 ħ 2次，得到C-H活化产物的反式（P -我镨3）2 NiH（2,3,5,6-C 6 F 4 H）。即使在100°C下加热数小时，也无法获得热力学C-F活化产物。与1,2,3,5-C 6 F 4 H的相似反应2和五氟苯产生所需的CH活化产物，反式-（P i Pr 3）2 NiH（2,3,4,6-C 6 F 4 H）和反式-（P i Pr 3）2 NiH（C
• A Combined Experimental and Computational Study of Unexpected C−F Bond Activation Intermediates and Selectivity in the Reaction of Pentafluorobenzene with a (PEt₃)₂Ni Synthon
  作者：Samuel A. Johnson、Erin T. Taylor、Sean J. Cruise

  DOI：10.1021/om900176v

  日期：2009.7.13

  accelerate the rate of C−F bond activation. The reaction of (PEt3)4Ni with C6F5H under similar conditions also provided spectroscopic evidence for the presence of the binuclear adduct [(PEt3)2Ni]2(μ-η2:η2-C6F5H), the mononuclear adduct (PEt3)2Ni(η2-C6F5H), and the C−H activation product trans-(PEt3)2NiH(C6F5) in the reaction mixture; however, unlike the C−F bond activation observed from pure [(PEt3

  蒽加合物（PET反应3）2的Ni（η 2 -C 14 ħ 10）以C 6 ˚F 5 H或C 1 6 ˚F 6提供了一种容易的路线可分离双核加合物[（PET 3）2的Ni] 2（μ-η 2：η 2 -C 6 ˚F 5 H）和[（PET 3）2的Ni] 2（μ-η 2：η 2 -C 6 ˚F 6）。Ni（PEt 3）2部分位于氟芳烃环的相对面上，并且键的长度表明芳香性的相当大的损失。[（PET解3）2的Ni] 2（μ-η 2：η 2 -C 6 ˚F 5为H）。C添加6 ˚F 5具有> 97％的选择性ħ转换到邻-F活化的化合物TRAN S-（ PEt 3）2 NiF（2,3,4,5-C 6 F 4 H）。向[（PEt 3）2 Ni] 2的溶液中添加C 6 F 5 H（μ-η 2：η 2 -C 6 ˚F 5 1H）还提供了平衡量的单核络合物（PET的3）2的Ni（η 2 -C 6 ˚F 5 H）与C-H活化产物反式-（PET