(η5-(1-(η5-cyclopentadienyl))-1-nickelafluorenyl)lithium(dimethoxyethane) | 1025484-78-9

• 英文名称: (η5-(1-(η5-cyclopentadienyl))-1-nickelafluorenyl)lithium(dimethoxyethane)
• 英文别名: 9-nickelafluorenyllithium(DME)
• CAS: 1025484-78-9
• 化学式: C₂₁H₂₃LiNiO₂
• 分子量: 373.043
• InChiKey: HEPCGFHKBCCOPC-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：

  1,3-双(2,4,6-三甲基苯基)氯化咪唑 、 (η5-(1-(η5-cyclopentadienyl))-1-nickelafluorenyl)lithium(dimethoxyethane) 以 四氢呋喃 为溶剂， 反应 24.0h， 以76%的产率得到1,3-bis(2,4,6-trimethylphenyl)-imidazolium 9-nickelafluorenyl
  参考文献：
  名称：

  新型的咪唑鎓和咪唑啉鎓盐，含9-尼克芴基阴离子-合成，结构和反应性†

  摘要：

  卡宾配合物的性质研究是现代配位化学最重要的领域之一。在本文中，我们提出了NHC-镍化合物的方便合成方法。9-镍芴基锂络合物与咪唑鎓或咪唑啉鎓盐反应，通过离子复分解反应获得9-镍芴基-NHC盐，收率非常好（66-92％）。这些化合物可以在高温下异构化，从而可能通过镍介导的氢转移至联苯部分，从而以优异的产率（88-91％）得到Ni-NHC复合物。在该反应中，镍环环本身在卡宾前体的去质子化中用作碱。DFT计算显示出合成盐的热力学不稳定性，吉布斯自由能差为1 -84千焦耳摩尔-1在298K和-167千焦摩尔-1在374 K.将所得到的盐和碳烯配合物在固体状态下相对空气和湿气是稳定的。

  DOI：

  10.1039/c4dt03786c
• 作为产物：
  描述：

  [(1-(η5-cyclopentadienyl)-1-nickelafluorenyl][lithium(dimethoxyethane)3] 以 neat (no solvent, solid phase) 为溶剂， 生成 (η5-(1-(η5-cyclopentadienyl))-1-nickelafluorenyl)lithium(dimethoxyethane)
  参考文献：
  名称：

  Synthesis and Structures of 9-Nickelafluorenyllithium Complexes

  摘要：

  A novel lithium biphenyl-2,2'-diyl(cyclopentadienyl)nickelate compound (9-nickelafluorenyllithium complex), ether)(2) (1), was prepared in the reaction between 2,2' dilithiobiphenyl and nickelocene in diethyl ether. Compound 1 was transformed to other 9-nickelafluorenyllithium compounds, [(1-(eta(5)-cyclopentadienyl))-1-nickelafluorenyl][lithium-(dimethoxyethane)(3)] (2) and (eta(5-)(1-(eta(5)-cyclopentadienyl))-1-nickelafluorenyl)lithium(dimethoxyethane) (3), whose crystal and molecular structures were determined by single-crystal X-ray analysis.

  DOI：

  10.1021/om701275u

文献信息

• Novel 9-Nickelafluorenyl Sandwich Complexes of Nickel(II) and Cobalt(II)
  作者：Piotr Buchalski、Ilona Grabowska、Anna Karaskiewicz、Kinga Suwińska、Lucjan Jerzykiewicz

  DOI：10.1021/om8002834

  日期：2008.7.1

  (9-Nickelafluorenyl)lithium was found to react with Ni(II) and Co(II) salts to form novel complexes in which the Ni or Co central metal atom is bonded to two nickelafluorenyl ligands. The crystal and molecular structures of the products were determined by single-crystal X-ray analysis.

  发现（9-镍芴基）锂与Ni（II）和Co（II）盐反应形成新的络合物，其中Ni或Co中心金属原子键合到两个镍芴基配体上。通过单晶X射线分析确定产物的晶体和分子结构。
• Nickelacyclic-Cobaltocene vs. Nickelacyclic-Nickelocene. Synthesis, X-ray Structures, Electron Transfer Activity, EPR Spectroscopy, and Theoretical Calculations
  作者：Piotr Buchalski、Elżbieta Kamińska、Katarzyna Piwowar、Kinga Suwińska、Lucjan Jerzykiewicz、Fulvio Rossi、Franco Laschi、Fabrizia Fabrizi de Biani、Piero Zanello

  DOI：10.1021/ic900329w

  日期：2009.6.1

  Reactions of 9-nickelafluorenyllithium with cobalt and nickel pentamethylcyclopentadienyl-acetylacetonates resulted in the formation of the novel nickelacyclic-cobaltocene 2 and nickelacyclic-nickelocene 3, respectively, in which the central metal atom is bonded to the nickelafluorenyl ring. On the basis of their redox propensity, compounds 2 and 3 were oxidized to the corresponding monocations [2](+) and [3](+). The crystal and molecular structures of both the redox couples were determined by single-crystal X-ray analysis. In spite of their structural similarity, they display a rather different electron transfer ability. To throw light on such an aspect, the pertinent redox couples have been examined by EPR spectroscopy and the nature of the frontier orbitals involved in the redox activity of the neutral precursors has been supported by extended Hckel theoretical calculations.