(η5-Cp)Ni(1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene)(Cl) | 858345-70-7

• 英文名称: (η5-Cp)Ni(1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene)(Cl)
• 英文别名: (η5-cyclopentadienyl)(1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene)chloronickel(II)；(η⁵-Cp)Ni(1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene)(Cl)；[cyclopentadienylNiCl(1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene)]；Ni{1,3-bis-(2,6-diisopropylphenyl)imidazol-2-ylidene}Clcyclopentadienyl；(η⁵-Cp)Ni(IPr)(Cl)；[CpNiCl(IDipp)]；[Ni(1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)Cl(η5-C5H5)]
• CAS: 858345-70-7
• 化学式: C₃₂H₄₁ClN₂Ni
• 分子量: 547.834
• InChiKey: CHNJSUZEWAUTCY-UHFFFAOYSA-M

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：

  (η5-Cp)Ni(1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene)(Cl) 在 potassium graphite 作用下， 以 四氢呋喃 为溶剂， 反应 72.0h， 以86%的产率得到(η⁵-Cp)Ni(1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene)
  参考文献：
  名称：

  通过有机金属镍（I）自由基进行的选择性P4活化：形成双核双磷化镍（II）以及相关的二卤化三卤化物和三卤化三卤化物。

  摘要：

  17e镍（I）自由基[CpNi（IDipp）]（1，IDipp = 1,3-双（2,6-二异丙基苯基）咪唑啉-2-亚烷基）与P4的反应生成四磷化镍[{CpNi（ IDipp）} 2（mu-eta（1）：eta（1）-P4）]与蝶形P4（2-）配体；与相关的硫族化物[{CpNi（IDipp）} 2（mu-E2）]（E = S，Se，Te）和[{CpNi（IDipp）} 2（mu-E3）]（E = S，Se）与S8，Seinfinity和Teinfinity。

  DOI：

  10.1039/c4cc02601b
• 作为产物：
  描述：

  1,3-双(2,6-二异丙基苯基)氯化咪唑鎓 、 nickelocene 以 四氢呋喃 为溶剂， 反应 20.0h， 生成 (η5-Cp)Ni(1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene)(Cl)
  参考文献：
  名称：

  LNi(Cp)X 与烷基氨基取代的 N-杂环卡宾配体 (L) 的配合物及其在 Suzuki-Miyaura 反应中的催化活性

  摘要：

  通式 LNi(Cp)X 的新型镍 ( ii ) 配合物（L 是 1,2,4-三唑或咪唑系列的 N-杂环卡宾 (NHC) 配体；Cp 是环戊二烯基阴离子；X = Cl， I) 被报道。在这些复合物中，NHC 配体 (L) 在杂环的 3 或 4 位含有烷基氨基。在 Suzuki-Miyaura 反应中测试合成的配合物和结构相似的没有烷基氨基的配合物的催化活性。引入烷基氨基进入NHC配体导致与配合物的催化活性的增强N，N' -diaryl取代NHC咪唑系列的配体并与所述复合物的活性的降低N，N'-二烷基取代的 1,2,4-三唑系列 NHC 配体。

  DOI：

  10.1007/s11172-021-3212-5
• 作为试剂：
  描述：

  4-氯苯丙酮 、 对溴甲苯 在 (η5-Cp)Ni(1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene)(Cl) 、 sodium t-butanolate 作用下， 反应 48.0h， 生成 1-(4-chlorophenyl)-2-(4-methylphenyl)-propan-1-one
  参考文献：
  名称：

  From acetone metalation to the catalytic α-arylation of acyclic ketones with NHC–nickel(ii) complexes

  摘要：

  空气稳定的NHC-镍（II）配合物在浓度低至1 mol％时，对非环状酮的α-芳基化反应表现出高催化活性。

  DOI：

  10.1039/c4cc00959b

文献信息

• Homogeneous Nickel Catalysts for the Selective Transfer of a Single Arylthio Group in the Catalytic Hydrothiolation of Alkynes
  作者：Denis A. Malyshev、Natalie M. Scott、Nicolas Marion、Edwin D. Stevens、Valentine P. Ananikov、Irina P. Beletskaya、Steven P. Nolan

  DOI：10.1021/om060302v

  日期：2006.9.1

  homogeneous catalytic system has been developed for the regioselective hydrothiolation of alkynes based on CpNi(NHC)Cl complexes (NHC = N-heterocyclic carbene). The designed catalyst was efficient for the selective addition of a single ArS group to an alkyne and was suitable for the synthesis of vinylsulfides, without side reactions leading to bis(arylthio)alkenes. Furthermore, this catalytic system allowed

  基于CpNi（NHC）Cl络合物（NHC = N-杂环卡宾），开发了一种用于炔烃的区域选择性氢硫醇化的新型均相催化体系。设计的催化剂可有效地将一个ArS基团选择性地添加到炔烃中，并且适合合成乙烯基硫化物，而不会产生导致双（芳硫基）烯烃的副反应。此外，该催化体系允许以高区域选择性（最高31：1）和良好收率（61-87％）的方式将S-H键加成至炔烃中。机理研究表明，该反应涉及三个步骤：（1）用镍基氯化物取代ArS基团；（2）炔烃插入Ni-S键中；以及（3）Ni-C键的质子分解。通过X射线分析明确表征了中间体CpNi（NHC）（SAr）配合物。
• Nickel(I) Monomers and Dimers with Cyclopentadienyl and Indenyl Ligands
  作者：Jianguo Wu、Ainara Nova、David Balcells、Gary W. Brudvig、Wei Dai、Louise M. Guard、Nilay Hazari、Po-Heng Lin、Ravi Pokhrel、Michael K. Takase

  DOI：10.1002/chem.201305021

  日期：2014.4.25

  SIPr) generates unusual 17 valence electron NiI monomers of the form (η5‐Cp)Ni(NHC) (NHC=IPr (3 a) or SIPr (3 b)) or (η5‐Ind)Ni(NHC) (NHC=IPr (4 a) or SIPr (4 b)), which have nonlinear geometries. A combination of DFT calculations and NBO analysis suggests that the NiI monomers are more strongly stabilized by the Cp ligand than by the indenyl ligand, which is consistent with experimental results. These

  （μ-Cl）2 Ni 2（NHC）2（NHC = 1,3-二（2,6-二异丙基苯基）-1,3-二氢-2 H-咪唑-2-亚烷基（IPr）或1的反应与一当量的环戊二烯基钠（NACp）或锂茚基（LiInd）形成的3,3-双（2,6-二异丙基苯基）咪唑烷基-2-亚基（SIPr）导致形成抗磁性NHC负载的Ni I二聚体（μ‐Cp）（μ‐Cl）Ni 2（NHC）2（NHC = IPr（1 a）或SIPr（1 b）; Cp = C 5 H 5）或（μ‐Ind）（μ‐Cl）Ni 2（NHC）2（NHC = IPr（2 a）或SIPr（2 b）; Ind ＝ C 7 H 9），其包含桥连的Cp和茚基配体。NACP或LiInd和（μ-Cl）的两个当量之间的相应反应2的Ni 2（NHC）2（NHC =或的IPr SIPR）生成不寻常的17价电子的Ni我的形式（η的单体5 -Cp）的Ni（NHC ）（NHC =
• Unsaturated dinickel–molybdenum clusters with N-heterocyclic carbene ligands
  作者：Sandra Milosevic、Eric Brenner、Vincent Ritleng、Michael J. Chetcuti

  DOI：10.1039/b800747k

  日期：——

  The first examples of mixed metal trinuclear clusters carrying N-heterocyclic carbene (NHC) ligands were isolated from reactions of the complexes [Ni(NHC)ClCp] [NHC = bis-(2,6-diisopropylphenyl)- or bis-(2,4,6-trimethylphenyl)-imidazol-2-ylidene] with [Mo(CO)(3)Cp](-); the unsaturated 46-electron clusters have triangular MoNi(2) cores and the reaction pathway activates usually inert Ni-Cp and Ni-NHC

  从配合物[Ni（NHC）ClCp] [NHC =双-（2,6-二异丙基苯基）-或双-（2， 4,6-三甲基苯基）-咪唑-2-亚烷基]与[Mo（CO）（3）Cp]（-）; 不饱和46电子簇具有三角形的MoNi（2）核，反应路径通常激活惰性的Ni-Cp和Ni-NHC键。
• Synthesis, Structure, and Solution Dynamics of Pentamethylcyclopentadienyl Nickel Complexes Bearing N-Heterocyclic Carbene Ligands
  作者：Vincent Ritleng、Caroline Barth、Eric Brenner、Sandra Milosevic、Michael J. Chetcuti

  DOI：10.1021/om800376q

  日期：2008.8.1

  Neutral pentamethylcyclopentadienyl nickel complexes of general formula [Ni(NHC)x(eta(5)-C5Me5)] [NHC = 1,3-dimethylimidazol-2-ylidene (Me-NHC), 1,3-bis(2,4,6,-trimethylphenyl)imidazol-2-ylidene (Mes-NHC), 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (iPr-NHC); X = Cl, 1] were prepared from the reaction of pentamethylcyclopentadienyl acetylacetonate nickel(II) with I equiv of the corresponding imidazolium salt (NHC center dot HX). The new complexes [Ni(Me-NHC)I(eta(5)-C5Me5)]1a, [Ni(Mes-NHC)Cl(eta(5)-C5Me5)] 2, and [Ni(iPr-NHC)Cl(eta(5)-C5Me5)] 3 were obtained in moderate to good yields and were fully characterized by C-13 and H-1 NMR spectroscopy, and in the cases of la and 2 by single-crystal X-ray crystallography. The related cyclopentadienyl complex [Ni(Me-NHC)I(eta(5)-C5H5)] 1b was also synthesized and structurally characterized; its geometry and spectroscopic data are comparable to those of complex la. The variable-temperature (VT) H-1 NMR spectra of the sterically constrained complexes 2 and 3 are consistent with restricted rotation about the nickel-carbene carbon bond. The free energy of activation for the dynamic processes, in both cases, was determined to be on the order of 65-67 U mol(-1) by VT NMR experiments.
• Microwave-assisted synthesis of (N-heterocyclic carbene)Ni(Cp)Cl complexes
  作者：Brant Landers、Oscar Navarro

  DOI：10.1016/j.ica.2011.09.055

  日期：2012.1

  The use of microwave heating for the synthesis of a series of (N-heterocyclic carbene)Ni(Cp)Cl complexes is presented. This protocol allows for a considerable reduction of the reaction times required using conventional heating, while affording comparable or better yields of the desired complexes. Their application as pre-catalysts in the microwave-assisted anaerobic oxidation of secondary alcohols is also discussed. (C) 2011 Elsevier B.V. All rights reserved.