bis[N,N'-(2,6-diisopropylphenyl)imino]acenaphthene nickel(II) dibromide | 163893-70-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 吖萘类
• 英文名称: bis[N,N'-(2,6-diisopropylphenyl)imino]acenaphthene nickel(II) dibromide
• 英文别名: {bis[N,N′-(2,6-diisopropylphenyl)imino]acenaphthene}dibromonickel；(1,2-bis(2,6-diisopropylphenylimino)acenaphthylenylidene)NiBr2；[1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene]NiBr2；dipp-BIANNiBr2；[2,6-iPr2C6H3-BIAN]NiBr2；Brookhart's catalyst
• CAS: 163893-70-7
• 化学式: C₃₆H₄₀Br₂N₂Ni
• 分子量: 719.225
• InChiKey: LCBLZTYQLWGBGI-BOXWNSCSSA-L

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：

  bis[N,N'-(2,6-diisopropylphenyl)imino]acenaphthene nickel(II) dibromide 在 甲基溴化镁 作用下， 以 乙醚 为溶剂， 生成 [C₃₆H₄₀N₂Ni(CH₃)2]
  参考文献：
  名称：

  Low-Temperature Spectroscopic Observation of Chain Growth and Migratory Insertion Barriers in (α-Diimine)Ni(II) Olefin Polymerization Catalysts

  摘要：

  DOI：

  10.1021/ja991931h
• 作为产物：
  描述：

  3,8-dimethoxyacenaphthenequinone 在 溶剂黄146 作用下， 以 乙腈 为溶剂， 反应 2.0h， 生成 bis[N,N'-(2,6-diisopropylphenyl)imino]acenaphthene nickel(II) dibromide
  参考文献：
  名称：

  骨架取代基对α-二亚胺Pd（II）和Ni（II）催化剂乙烯（Co）聚合性能的影响

  摘要：

  A series of alpha-diimine ligands with different substituents on the acenaphthyl backbone were synthesized and characterized. The corresponding Ni(II) and Pd(II) complexes were prepared and used in ethylene polymerization and copolymerization with methyl acrylate. In ethylene polymerization, these Ni(II) complexes showed activities of up to 1.6 x 10(7) g/((mol of Ni) h), generating polyethylene with a molecular weight (M-n) of up to 4.2 x 10(5). Interestingly, these Ni(II) complexes behave very similarly in ethylene polymerization except for the complex with two methoxy substituents on the ortho position of the acenaphthyl backbone, in which case about 3 times higher polyethylene molecular weight and much lower branching density were observed. The ligand substituent effect is much more dramatic for the Pd(II) complexes. In ethylene polymerization, activities of up to 1.7 x 10(5) g/((mol of Pd) h) and a polyethylene molecular weight (M-n) of up to 4.7 x 10(4) could be obtained. The Pd(II) complex with two methoxy substituents on the ortho position of the acenaphthyl backbone demonstrated much higher activity and generated polyethylene with about 3 times higher molecular weight than that for the classic Pd(II) complex. A similar trend was maintained in ethylene methyl acrylate copolymerization.

  DOI：

  10.1021/acs.organomet.6b00202

文献信息

• Chain-Walking Polymerization of Linear Internal Octenes Catalyzed by <i>α-</i>Diimine Nickel Complexes
  作者：Fuzhou Wang、Ryo Tanaka、Qingshan Li、Yuushou Nakayama、Takeshi Shiono

  DOI：10.1021/acs.organomet.8b00042

  日期：2018.5.14

  The chain-walking polymerization of linear internal alkenes (i.e., trans-2-, 3-, and 4-octenes) using α-diimine nickel catalysts activated with modified methylaluminoxane (MMAO) was studied in comparison with the corresponding terminal alkene polymerization. The rates of polymerization were found to decrease in the following order: 1-octene > 4-octene ≥ 2-octene ≫ 3-octene. The obtained branched poly(2-octene)s

  与相应的末端烯烃聚合相比，研究了使用改性甲基铝氧烷（MMAO）活化的α-二亚胺镍催化剂对线性内部烯烃（即反式-2-，3-和4-辛烯）的链走聚合。发现聚合速率按以下顺序降低：1-辛烯> 4-辛烯≥2-辛烯≫3-辛烯。所得的高分子量且M w / M n小于2的支链聚（2-辛烯）和聚（4-辛烯）是玻璃化转变温度（T g）约为-66°C。在0°C，4-辛烯以活性/受控方式聚合。聚合物的NMR分析表明，由于单体的异构化作用，4-辛烯的链行走聚合产生具有恒定支化密度的周期性支化的聚合物，而2-辛烯的链行走聚合得到的聚合物具有比预期值更少的支链。的（Ñ 2），（Ñ 3） -和（Ñ 3），（Ñ 2）内部（的-insertions Ñ 2） -烯烃[CH 3（CH 2）Ñ CH = CH（CH 2）m CH 3 ]然后链式走动被13产生的聚合物的13 C NMR分析。
• Simple and Strong Dative Attachment of α-Diimine Nickel (II) Catalysts on Supports for Ethylene Polymerization with Controlled Morphology
  作者：Ehsan Kianfar、Reza Azimikia、Seyed Mohammad Faghih

  DOI：10.1007/s10562-020-03116-z

  日期：2020.8

  naphthoquinone Nickel dibromide(d) showed the highest activity among other evaluated homogeneous catalysts, its MgCl 2 supported catalyst (d/S-MgCl 2 ) has shown the highest activity among MgCl 2 supported catalysts too. These MgCl 2 supported catalysts were pre-polymerized in presence of ethylene monomer in the mild polymerization condition to yield a pre-polymerized catalyst with polymer/catalyst weight

  摘要 本文报道了新型球形MgCl 2 负载α-二亚胺镍（II）催化剂的制备，用于淤浆相乙烯聚合。α-二亚胺配体是通过 2, 6-二取代烷基或芳基苯胺与对位具有羟基官能团的 Ace 萘醌的缩合反应合成的。羟基官能化的α-二亚胺通过配价键牢固地附着在球形MgCl 2 载体表面上。不需要连接剂将复合物连接到载体表面，并且负载镍的量是可控的，以改善聚合物粉末的形态，尤其是堆积密度。当均相催化剂负载在二氧化硅上时，催化剂活性会显着降低，但当它们负载在经过热处理的球形 MgCl 2 上时，这种降低会降低。作为均相双(N,N'-(4-(3-羟基-丙基)-2,6-二[(4-叔丁基-苯基)-苯基)氨基]乙酰萘醌二溴化镍(d)表现出最高在其他评价的均相催化剂中，其 MgCl 2 负载型催化剂（d/S-MgCl 2 ）在 MgCl 2 负载型催化剂中也表现出最高的活性。条件产生聚合物/催化剂重量比等于 6 的预
• Mechanistic Studies of Nickel(II) Alkyl Agostic Cations and Alkyl Ethylene Complexes:  Investigations of Chain Propagation and Isomerization in (α-diimine)Ni(II)-Catalyzed Ethylene Polymerization
  作者：Mark D. Leatherman、Steven A. Svejda、Lynda K. Johnson、Maurice Brookhart

  DOI：10.1021/ja021071w

  日期：2003.3.1

  addressed using NMR line broadening techniques. Trapping of these complexes with ethylene provides cationic Ni alkyl ethylene species, which are used to determine rates of ethylene insertion into primary and secondary carbon centers. The Ni agostic alkyl cations are also trapped by CH(3)CN and Me(2)S to yield Ni(R)(L)(+) (L = CH(3)CN, Me(2)S) complexes, and the dynamic behavior of these species in the

  介绍了一系列 (α-二亚胺) NiR(2) (R = Et, (n)Pr) 配合物通过相应 (α-二亚胺) NiBr(2) 前体的格氏烷基化的合成。这些物质在低温下被氧鎓酸 [H(OEt(2))(2)](+)[BAr'(4)](-) 质子化产生阳离子 Ni(II) β-agostic 烷基配合物，其模型相关存在于镍催化烯烃聚合反应中的中间体。使用 NMR 谱线展宽技术定量地解决了这些兴奋性烷基阳离子的高度动态特性。这些复合物与乙烯的捕获提供了阳离子 Ni 烷基乙烯物质，用于确定乙烯插入伯碳中心和仲碳中心的速率。Ni 积极的烷基阳离子也被 CH(3)CN 和 Me(2)S 捕获以产生 Ni(R)(L)(+) (L = CH(3)CN, Me(2)S) 络合物，并讨论了这些物种在不同 [L] 存在下的动态行为。从这些实验中获得的动力学数据用于展示（α-二亚胺）Ni 催化剂的乙烯聚合机理的整体图
• Novel phenolic antioxidant-functionalized dendritic polyethylene: Synthesis by tailor-made nickel(II) α-diimine-catalyzed copolymerization and its characteristics as non-releasing additive
  作者：Zahra Balzadeh、Hassan Arabi

  DOI：10.1016/j.reactfunctpolym.2016.11.005

  日期：2017.2

  This work describes a simple one-pot and controlled synthetic method to generate migration-resistant bio-friendly tailor-made antioxidants through ethylene–sterically hindered phenolic antioxidant (SHPA) copolymerization by coordination polymerization using MAO-activated nickel(II)-α-diimine catalyst. The antioxidant tethering into the polymer chain by chain walking catalysts leads to adjustable copolymer

  这项工作描述了一种简单的一锅可控合成方法，该方法通过使用MAO活化的镍（II）-α-二亚胺配位聚合，通过乙烯-位阻酚类抗氧化剂（SHPA）共聚生成耐迁移的生物友好量身定制的抗氧化剂。催化剂。通过链走催化剂将抗氧化剂束缚到聚合物链中，导致可调节的共聚物结构具有不同的热特性。已经发现，氧化诱导时间可以被微调（从2到36分钟）通过适当SHPA内容选择和P Ë改变（从10 bar到0.5 bar）。此外，DPE-SHPA共聚物的化学成分分析显示，除了树状结构外，每1000个碳原子包含123个分支和类似于半球形拓扑的AFM图像，SHPA掺入量为0.6 wt％（约80％转化率）。还研究了合成共聚物的抗迁移性及其作为非释放性添加剂的应用。
• Cationic methallylnickel(II) complexes with α-diimine ligands: synthesis and X-ray structure
  作者：Ali Mechria、Claude Bavoux、Faouzi Bouachir

  DOI：10.1016/s0022-328x(03)00345-0

  日期：2003.7

  α-diimine ligands ArNC(R)C(R)NAr react with Ni(COD)2 (2) in the presence of methallyloxyphosphonium hexafluorophosphate [CH2C(Me)CH2OP(NMe2)3]+·PF6− (3) to give new cationic methallyl complexes of nickel(II) with α-diimine ligands 4a and 4b. The same complexes 4a–d can also be generated in high yields by reacting [α-diimine] NiBr2 with zinc and methallyloxyphosphonium salt 3. Molecular structure

  α-二亚胺配体ArNC（R）C（R）NAr用Ni（COD）反应2（2在存在methallyloxyphosphonium六氟磷酸盐[CH）2 C（Me）的CH 2 O P（NME 2）3 ] + ·PF 6 - （3），得到镍的新的阳离子甲代烯丙基络合物（Ⅱ）与α二亚胺配体图4a和4b中。通过使[α-二亚胺] NiBr 2与锌和甲基烯丙氧基phosph盐3反应，也可以高收率产生相同的络合物4a - d。4a的分子结构 通过单晶X射线衍射确定。