Ni(cyclopentadienyl)(Cl)[1,3-bis-(2,4,6-trimethylphenyl)-4,5-dihydroimidazole-2-ylidene)] | 858345-69-4

• 英文名称: Ni(cyclopentadienyl)(Cl)[1,3-bis-(2,4,6-trimethylphenyl)-4,5-dihydroimidazole-2-ylidene)]
• 英文别名: CpNi(1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene)Cl；CpNi(N,N'-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene)Cl；(SIMes)Ni(Cp)Cl；NiCp(Cl)(SIMes)；Cp(SIMes)NiCl
• CAS: 858345-69-4
• 化学式: C₂₆H₃₁ClN₂Ni
• 分子量: 465.689
• InChiKey: QYOOZDRFJUBKNO-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：

  Ni(cyclopentadienyl)(Cl)[1,3-bis-(2,4,6-trimethylphenyl)-4,5-dihydroimidazole-2-ylidene)] 、 silver trifluoroacetate 以 四氢呋喃 、 乙腈 为溶剂， 反应 1.0h， 以63%的产率得到[Ni(η⁵-C5H5)(CF3COO)(1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene)]
  参考文献：
  名称：

  Anion exchange in [Ni(η5-C5H4R)(Cl)(NHC)]. Counterion effect on the structure and catalytic activity

  摘要：

  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。

  DOI：

  10.1039/c3dt53352b
• 作为产物：
  描述：

  1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolium chloride 、 nickelocene 以 四氢呋喃 为溶剂， 以87%的产率得到Ni(cyclopentadienyl)(Cl)[1,3-bis-(2,4,6-trimethylphenyl)-4,5-dihydroimidazole-2-ylidene)]
  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

• Nickel alkynyl and allenylidene complexes: Synthesis and properties
  作者：Thomas Haas、Katrin Kaspar、Konstanze Forner、Matthias Drexler、Helmut Fischer

  DOI：10.1016/j.jorganchem.2010.10.041

  日期：2011.2

  alkynyl complexes [Cp(PPh3)Ni–CC–C(O)R]. Subsequent O-methylation with either [Me3O]BF4 or MeSO3CF3 affords cationic allenylidene complexes, [Cp(PPh3)NiCCC(OMe)R]+X¯ (X = BF4, SO3CF3). N-Alkylation of Cp(PPh3)Ni-pyridylethynyl complexes likewise gives cationic allenylidene complexes. [Cp(PPh3)Ni–CC–C(CH)4N] adds BF3 at nitrogen. Modification of the ligand sphere in these nickel allenylidene complexes

  铜催化的[Cp（PPh 3）NiCl]与末端炔烃H C C C（O）R（R = O-甲基，NMe 2，Ph）生成炔基配合物[Cp（PPh 3）Ni –C C–C（O）R]。随后用[Me 3 O] BF 4或MeSO 3 CF 3进行O-甲基化可得到阳离子亚烯基络合物，[Cp（PPh 3）Ni C C C（OMe）R] + X（X = BF 4，SO 3 CF 3）。Cp（PPh 3的N-烷基化Ni-吡啶基乙炔基络合物同样产生阳离子亚烯基络合物。[Cp（PPh 3）Ni–C C–C（CH）4 N]在氮气中添加BF 3。通过在炔基络合物前体中用PMe 3代替PPh 3，可以修饰这些镍烯基亚烷基络合物中的配体球。通过[Cp（SIMes）NiCl]与HC C–C（O）NMe的连续反应可得到第一个烯基（碳烯）镍阳离子[Cp（SIMes）N C C C（OMe）NMe 2 ] + 2和[Me 3 O]
• 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。
• 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.
• N-Heterocyclic carbene complexes of cyclopentadienylnickel(II): Synthesis, structure and catalytic activity in styrene polymerization
  作者：Włodzimierz Buchowicz、Andrzej Kozioł、Lucjan B. Jerzykiewicz、Tadeusz Lis、Stanisław Pasynkiewicz、Aleksandra Pęcherzewska、Antoni Pietrzykowski

  DOI：10.1016/j.molcata.2006.05.061

  日期：2006.9

  Cyclopentadienylnickel(H) complexes with N-heterocyclic carbenes [NiCp(X)(NHC)] (X = Cl, Br or CH3), combined with MAO have been used as catalysts for the polymerization of styrene. The catalytic activity of the systems depended mainly on the ease of the abstraction of X substituent by MAO and the stabilization of cationic species [NiCp(NHC)](+). The molecular structures of three title complexes have been determined by single-crystal X-ray diffraction. All three compounds crystallize in monoclinic crystal system with four molecules in the unit cell. Their structural parameters have been compared with data reported for similar complexes. Two of these complexes [NiCp(CH3)(IMes)] and [NiCp(CH3)(SIMes)] are the first examples of structurally characterized (unsubstituted)-cyclopentadienylnickeI methyl compounds. (c) 2006 Elsevier B.V. All rights reserved.