[(IPr)Ni(styrene)₂]

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: [(IPr)Ni(styrene)₂]
• 化学式: C₄₃H₅₂N₂Ni
• 分子量: 655.589
• InChiKey: XGDHBKSQPMARPY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.12
• 重原子数：
  46
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [(IPr)Ni(styrene)₂] 、 异氰酸苯酯 以 四氢呋喃 为溶剂， 反应 2.0h， 以48%的产率得到
  参考文献：
  名称：

  苯基异（硫）氰酸酯与N-杂环碳基负载的镍配合物的反应：镍环的形成。

  摘要：

  The nickel(I) complex [(eta(5)-Cp)Ni(IPr)] (Cp = cyclopentadienyl, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) reacts with phenyl isothiocyanate to afford the new heteronickelacycle [(IPr)NiSC(NPh)N(Ph)CS] (1), which contains the novel bidentate and dianionic ligand {SC(NPh)N(Ph)CS}(2-). Complex 1 is also obtained from the nickel(0) compound [(IPr)-Ni(styrene)(2)] with two equivalents of PhNCS. The gamma-lactam-nickelacycle [(IPr)NiN(Ph)C(O)CH2CH(Ph) (3) is formed from [(IPr)Ni(styrene)(2)] and one equivalent of phenyl isocyanate. Complex 3 is a rare example of a nickel(II) complex with a T-shaped structure. Compounds 1 and 3 were characterized by X-ray crystallography, H-1 and C-13 NMR spectroscopy, UV-vis spectroscopy, and elemental analysis.

  DOI：

  10.1021/acs.organomet.6b00473
• 作为产物：
  描述：

  1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazole trafluoroborate 在 potassium tert-butylate 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 [(IPr)Ni(styrene)₂]
  参考文献：
  名称：

  用于烯烃异构化的模块化 Ni(0)/硅烷催化系统

  摘要：

  烯烃在所有化学领域中普遍用作起始材料和合成目标。控制它们沿链的几何形状和位置对于它们的反应性和特性至关重要，但仍然具有挑战性。烯烃异构化是一种合成目标烯烃的原子经济过程，可以使用过渡金属催化剂控制选择性。温和、选择性异构化反应性的发展为烯烃的远程官能化提供了高效的串联催化系统，在该过程中，起始烯烃在官能化步骤之前被异构化到新的位置。开发用于远程功能化应用的异构化催化剂的主要挑战是（i）催化剂结构缺乏模块化和（ii）在催化剂活化过程中需要非模块化和/或苛刻的添加剂。我们通过模块化 (NHC)Ni(0)/硅烷催化系统 (NHC,N-杂环卡宾），展示了使用三芳基硅烷和易于获得的 (NHC)Ni(0) 配合物原位形成所提出的活性 (NHC)(甲硅烷基)Ni-H 物质。我们表明，通过修饰辅助配体和硅烷配偶体来分别修饰催化剂的空间和电子性质是很容易实现的，创造了一种独特的多功能催化体系，可有效地形成具有高产率和选择性的内烯烃。E

  DOI：

  10.1021/acs.organomet.2c00010
• 作为试剂：
  描述：

  对甲苯亚磺酸苯酯 、 苯胺 在 [(IPr)Ni(styrene)₂] 、 lithium tert-butoxide 作用下， 以 1,4-二氧六环 为溶剂， 反应 10.0h， 以99%的产率得到二苯胺
  参考文献：
  名称：

  Synthesis, Structural Characterization, and Catalytic Activity of IPrNi(styrene)₂in the Amination of Aryl Tosylates

  摘要：

  A novel bis-styrene IPrNi0 derivative has been synthesized from the reaction of Ni(COD)(2) and free 1,3-bis(2,6-diisopropylphenyl)imidazolidene (IPr) ligand in the presence of styrene. The complex has been characterized by spectroscopic data as well as by X-ray crystallography. Its catalytic performance in the amination reaction of aryl tosylates is also reported. The catalytic reactions proceed in a very selective manner, affording moderate to high yields of cross-coupling products in short reaction times at 110 degrees C.

  DOI：

  10.1021/om300566m

文献信息

• Simplified and versatile access to low valent Ni complexes by metal-free reduction of Ni^II precursors
  作者：Emile Moser、Erwann Jeanneau、Nicolas Mézailles、Hélène Olivier-Bourbigou、Pierre-Alain R. Breuil

  DOI：10.1039/c9dt00668k

  日期：——

  The reduction of [Ni(DME)Cl2] with 2 equiv. of bis(trimethylsilyl)-1,4-tetramethyldihydropyrazine in the presence of a ligand L and an excess of olefin cleanly leads to [Ni(L)(alkene)2] complexes. When reduction is performed in the presence of 1,5-cyclooctadiene (COD), [Ni(COD)2] is obtained. Such an approach also allows access to the NiI dimer [Ni(bis(dicyclohexylphosphino)propane)Cl]2.

  用2当量还原[Ni（DME）Cl 2 ]。在配体L和过量烯烃的存在下，双（三甲基甲硅烷基）-1，4-四甲基二氢吡嗪的纯净地产生[Ni（L）（烯烃）2 ]络合物。当在1，5-环辛二烯（COD）存在下进行还原时，获得[Ni（COD）2 ]。这种方法还允许接近Ni I二聚体[Ni（双（二（二环己基膦基膦基）丙烷）Cl] 2。
• Disproportionation Reactions of an Organometallic Ni(I) Amidate Complex: Scope and Mechanistic Investigations
  作者：D. Dawson Beattie、Gautier Lascoumettes、Pierre Kennepohl、Jennifer A. Love、Laurel L. Schafer

  DOI：10.1021/acs.organomet.8b00074

  日期：2018.5.14

  result in disproportionation. In the case of CO we show that reactions in the solid state afford selectivity for and isolation of the reaction intermediate (IPr)Ni(κ1-N-N(iPr)C(O)tBu)(CO) ([2-CO]), which is not isolable by solution methods. Kinetic analysis of the disproportionation reaction with alkenes suggests that the reaction is first order in both nickel and alkene. Preliminary trapping experiments

  所述N-杂环卡宾支持三维坐标的Ni（I）配合物（IPR）的Ni（κ 1 - ñ -N（我PR）C（O）吨卜）（CNXyl）（[ 2-CNXyl ]; CNXyl = 2， 6-二甲基苯基异氰化物）与1当量的CNXyl歧化，得到等摩尔的Ni（0）和Ni（II）配合物（IPr）Ni（CNXyl）3（[ 3-CNXyl ]）和（IPr）Ni（κ 2 - N，O -N（i Pr）CO（t Bu））2（[ 4 ]）。当将2当量的异腈CNXyl添加到（IPr）Ni（κ）中时，也会生成复合物[ 3-CNXyl ]和[ 4 ]3 - N，双（H 2 C Me）-N（i Pr）C（O）t Bu）（[ 1 ]）。此外，我们表明与π受体CO和选择的烯烃的反应也导致歧化。在CO的情况下，我们表明，在固体状态下的反应得到的选择性和反应的隔离中间体（IPR）的Ni（κ 1 - ñ -N（我PR）C（O）吨卜）（CO）（[
• Modular Ni(0)/Silane Catalytic System for the Isomerization of Alkenes
  作者：Kiana E. Kawamura、Alison Sy-min Chang、Daryl J. Martin、Haley M. Smith、Parker T. Morris、Amanda K. Cook

  DOI：10.1021/acs.organomet.2c00010

  日期：2022.2.28

  versatile catalytic system that is effective for the formation of internal alkenes with high yield and selectivity for the E-alkene. The use of silanes as mild activators enables isomerization of substrates with a variety of functional groups, including acid-labile groups. The broad substrate scope, enabled by catalyst design, makes this catalytic system a strong candidate for use in tandem catalytic applications

  烯烃在所有化学领域中普遍用作起始材料和合成目标。控制它们沿链的几何形状和位置对于它们的反应性和特性至关重要，但仍然具有挑战性。烯烃异构化是一种合成目标烯烃的原子经济过程，可以使用过渡金属催化剂控制选择性。温和、选择性异构化反应性的发展为烯烃的远程官能化提供了高效的串联催化系统，在该过程中，起始烯烃在官能化步骤之前被异构化到新的位置。开发用于远程功能化应用的异构化催化剂的主要挑战是（i）催化剂结构缺乏模块化和（ii）在催化剂活化过程中需要非模块化和/或苛刻的添加剂。我们通过模块化 (NHC)Ni(0)/硅烷催化系统 (NHC,N-杂环卡宾），展示了使用三芳基硅烷和易于获得的 (NHC)Ni(0) 配合物原位形成所提出的活性 (NHC)(甲硅烷基)Ni-H 物质。我们表明，通过修饰辅助配体和硅烷配偶体来分别修饰催化剂的空间和电子性质是很容易实现的，创造了一种独特的多功能催化体系，可有效地形成具有高产率和选择性的内烯烃。E
• Synthesis, Structural Characterization, and Catalytic Activity of IPrNi(styrene)₂in the Amination of Aryl Tosylates
  作者：María José Iglesias、Juan F. Blandez、Manuel R. Fructos、Auxiliadora Prieto、Eleuterio Álvarez、Tomás R. Belderrain、M. Carmen Nicasio

  DOI：10.1021/om300566m

  日期：2012.9.10

  A novel bis-styrene IPrNi0 derivative has been synthesized from the reaction of Ni(COD)(2) and free 1,3-bis(2,6-diisopropylphenyl)imidazolidene (IPr) ligand in the presence of styrene. The complex has been characterized by spectroscopic data as well as by X-ray crystallography. Its catalytic performance in the amination reaction of aryl tosylates is also reported. The catalytic reactions proceed in a very selective manner, affording moderate to high yields of cross-coupling products in short reaction times at 110 degrees C.
• Reaction of Phenyl Iso(thio)cyanate with N-Heterocyclic Carbene-Supported Nickel Complexes: Formation of Nickelacycles
  作者：Stefan Pelties、Robert Wolf

  DOI：10.1021/acs.organomet.6b00473

  日期：2016.8.22

  The nickel(I) complex [(eta(5)-Cp)Ni(IPr)] (Cp = cyclopentadienyl, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) reacts with phenyl isothiocyanate to afford the new heteronickelacycle [(IPr)NiSC(NPh)N(Ph)CS] (1), which contains the novel bidentate and dianionic ligand SC(NPh)N(Ph)CS}(2-). Complex 1 is also obtained from the nickel(0) compound [(IPr)-Ni(styrene)(2)] with two equivalents of PhNCS. The gamma-lactam-nickelacycle [(IPr)NiN(Ph)C(O)CH2CH(Ph) (3) is formed from [(IPr)Ni(styrene)(2)] and one equivalent of phenyl isocyanate. Complex 3 is a rare example of a nickel(II) complex with a T-shaped structure. Compounds 1 and 3 were characterized by X-ray crystallography, H-1 and C-13 NMR spectroscopy, UV-vis spectroscopy, and elemental analysis.