CpNi(1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene)Cl | 858345-71-8

• 英文名称: CpNi(1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene)Cl
• 英文别名: CpNi(N,N'-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene)Cl；(SIPr)Ni(Cp)Cl
• CAS: 858345-71-8
• 化学式: C₃₂H₄₃ClN₂Ni
• 分子量: 549.85
• InChiKey: XFHULCOGEUSLAS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• 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：

  CpNi(1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene)Cl 、 苯硫酚 在 三乙胺 作用下， 以 甲苯 为溶剂， 以89%的产率得到CpNi(N,N'-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene)(SPh)
  参考文献：
  名称：

  炔烃催化加氢硫醇化反应中单个芳硫基选择性转移的均相镍催化剂

  摘要：

  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。

  DOI：

  10.1021/om060302v
• 作为产物：
  描述：

  1,3-双-(2,6-二异丙基苯基)咪唑鎓氯化物 、 nickelocene 以 四氢呋喃 为溶剂， 以81%的产率得到CpNi(1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene)Cl
  参考文献：
  名称：

  Simple Synthesis of CpNi(NHC)Cl Complexes (Cp = Cyclopentadienyl; NHC = N-Heterocyclic Carbene)

  摘要：

  The reaction of saturated and unsaturated imidazolium salts with nickelocene in refluxing THF results in the formation of NHC complexes of general formula CpNi(NHC)Cl (NHC = SIMes (2), IPr (3), SIPr (4)). This protonation Of CP2Ni was also tested using phosphonium salts, and the reaction of nickelocene with triethylphosphonium chloride leads to CpNi(PEt3)Cl (5). All compounds were characterized by NMR and X-ray crystallography. The catalytic activity of the NHC compounds was tested in aryl amination (Buchwald-Hartwig reaction) and in aryl halide dehalogenation reactions.

  DOI：

  10.1021/om0501879

文献信息

• Anion exchange in [Ni(η5-C5H4R)(Cl)(NHC)]. Counterion effect on the structure and catalytic activity
  作者：Włodzimierz Buchowicz、Łukasz Banach、Joanna Conder、Piotr A. Guńka、Dominik Kubicki、Piotr Buchalski

  DOI：10.1039/c3dt53352b

  日期：——

  A series of novel complexes [Ni(η5-C5H4R)(L)(NHC)]+A−2a–2j and [Ni(η5-C5H5)(A)(NHC)] 3a–3c has been obtained by anion metathesis from the corresponding chlorides 1a–1d, depending on the anion binding properties and reaction conditions. Solid-state structures of two cationic complexes (2c, 2j) and two complexes with a coordinated anion (3a, 3c) have been determined by X-ray diffraction revealing a trigonal planar geometry in all cases. Unexpectedly, 3c displayed unprecedented for this type of compounds temperature-dependent NMR spectra that were interpreted in terms of spin equilibrium. The cationic complexes 2 were less efficient in styrene polymerization than the parent chlorides 1. However, the activity of 2 and 3 in Suzuki cross-coupling did not depend considerably on the counterion.

  根据阴离子的结合特性和反应条件，通过阴离子偏合成从相应的氯化物 1aâ1d 得到了一系列新型配合物 [Ni(δ-5-C5H4R)(L)(NHC)]+Aâ2aâ2j 和 [Ni(δ-5-C5H5)(A)(NHC)] 3aâ3c。通过 X 射线衍射测定了两种阳离子络合物（2c、2j）和两种配位阴离子络合物（3a、3c）的固态结构，发现所有络合物都具有三棱锥平面几何形状。出乎意料的是，3c 显示了该类化合物前所未有的温度依赖性核磁共振光谱，可以用自旋平衡来解释。阳离子配合物 2 在苯乙烯聚合过程中的效率低于母体氯化物 1。
• Metal‐Mediated Oligomerization Reactions of the Cyaphide Anion
  作者：Eric S. Yang、Daniel W. N. Wilson、Jose M. Goicoechea

  DOI：10.1002/anie.202218047

  日期：2023.3.6

  We describe three distinct oligomerization reactions of metal complexes bonded to the cyaphide ligand (CP−). Reductive coupling of a gold cyaphido complex was found to afford a species containing a C2P24− dimer. By contrast, sterically unprotected metal complexes with more polar M−CP (M=Ni, Sc) bonds were found to spontaneously oligomerize giving rise to species with bridging C2P22− and C3P33− ligands

  我们描述了与氰化物配体（CP - ）键合的金属配合物的三种不同的低聚反应。发现金 cyaphido 复合物的还原偶联可提供含有 C 2 P 2 4−二聚体的物质。相比之下，具有更多极性M​​−CP (M=Ni, Sc) 键的空间未保护的金属络合物被发现自发低聚，产生具有桥接C 2 P 2 2−和C 3 P 3 3−配体的物质。
• 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.