N,N'-bis(2,6-bis(4-tert-butylphenyl)phenyl)-1,4-diaza-2,3-dimethyl-butadiene | 340187-64-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N,N'-bis(2,6-bis(4-tert-butylphenyl)phenyl)-1,4-diaza-2,3-dimethyl-butadiene
• 英文别名: ((Me)CNC6H3(C6H4(t-Bu-4))2-2,6)；2-N,3-N-bis[2,6-bis(4-tert-butylphenyl)phenyl]butane-2,3-diimine
• CAS: 340187-64-6
• 化学式: C₅₆H₆₄N₂
• 分子量: 765.138
• InChiKey: ZTXHSUWQFPYEDD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.5
• 重原子数：
  58
• 可旋转键数：
  11
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N,N'-bis(2,6-bis(4-tert-butylphenyl)phenyl)-1,4-diaza-2,3-dimethyl-butadiene 、 gallium(I) iodide 以 甲苯 为溶剂， 以36%的产率得到[GaI₂((Me)CNC₆H₃(C₆H₃-tBu-4)2-2,6)]
  参考文献：
  名称：

  Investigations into the preparation of groups 13–15 N-heterocyclic carbene analogues

  摘要：

  Attempts have been made to prepare a variety of groups 13 - 15 N-heterocyclic carbenoid systems. The work in group 13 led to two structurally characterized, paramagnetic gallium(III) heterocycles, [I2Ga{[N(R)C(Me)](2)}], R = C6H3Pr2i-2, 6 (Ar) or C6H3(C6H4Bu'-4)(2)-2,6. Reduction of the former gave the anionic gallium(I) heterocyclic complex, [K(tmeda)][:Ga{[N(Ar)C(Me)](2)}], which was oxidatively coupled, affording the structurally characterized digallane(4), [Ga{[N(Ar)C(Me)](2)}](2). From group 14, the new germanium(IV) heterocycle, [Cl2Ge{[N(Ar)C(H)](2)}], and the N-heterocyclic germylene, [:Ge{[N(Ar)C(H)](2)}], have been prepared and fully characterized. Attempts to prepare N-heterocyclic silylene, phosphenium and arsenium compounds were unsuccessful and led instead to the silyl, phosphino and arsino-substituted ene-amines, [(ClnE)(2){mu-[N(Ar)C(H)](2)}], E = Si, n = 3; E = P or As, n = 2. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2006.12.014
• 作为产物：
  描述：

  2,6-二溴苯胺 在 四(三苯基膦)钯 、 对甲苯磺酸 sodium carbonate 作用下， 以 乙醇 、 苯 为溶剂， 反应 88.0h， 生成 N,N'-bis(2,6-bis(4-tert-butylphenyl)phenyl)-1,4-diaza-2,3-dimethyl-butadiene
  参考文献：
  名称：

  新型镍（II）二亚胺配合物和催化剂设计对聚乙烯微观结构的控制

  摘要：

  以不同取代的硼酸作为通用构件，以简单、高产的路线合成了新的“邻芳基”α-二亚胺配体 ah。在二亚胺配体存在下，复合物前体二乙酰丙酮-镍 (II) 与三苯甲基盐（如 [CPh3] [B(C6F5)4] 或 [CPh3] [SbCl6]）的反应得到单阳离子方形平面复合物 2a -g 几乎是定量的产量。将合适的晶体 (2d',e,f,g) 提交给 X 射线衍射分析。开发了一种几何模型来描述影响聚合物微观结构的镍 (II) 中心周围配体碎片的取向。在升高的反应温度和压力下，在氢气存在下，2a-e 催化乙烯的均聚反应，得到从 HD- 到 LLD-PE 等级的支化 PE 产品。聚合结果表明根据特定的复杂取代进行精确微观结构控制的可能性。通过单轴拉伸对材料密度和机械性能的初步研究直至失效指向新的材料特性，该特性可由催化剂设计的简单乙烯单体产生。

  DOI：

  10.1021/ja070224i

文献信息

• Novel Non-Symmetric Nickel-Diimine Complexes for the Homopolymerization of Ethene: Control of Branching by Catalyst Design
  作者：Markus Schmid、Robert Eberhardt、Jürgen Kukral、Bernhard Rieger

  DOI：10.1515/znb-2002-1011

  日期：2002.10.1

  Non-symmetric diimine ligands (Ar-N=C(CH₃)-(CH₃)C=NAr*; Ar: 2,6-diisopropyl-phenyl; Ar*: 2,6-di(4-tert-butyl-phenyl)phenyl (4b), 2,6-di(4-OCH₃)-phenyl)phenyl (4c)) were synthesized and converted in-situ into the corresponding nickel dibromo complexes (5b, c) by reaction with (DME)NiBr₂. The complexes were activated for ethene polymerization by treatment with MAOat ambient temperature. The resulting highmolecular weight polymer products (M_W > 4.0 x 10⁶ g mol^-1) have a branched microstructure (predominantly methyl groups), as indicated by ¹³C NMR spectroscopy. The degree of branching can be controlled by a proper choice of the 2,6-diphenyl modified aniline moieties resulting in melting transitions ranging from 92 - 130 °C.

  非对称二亚胺配体（Ar-N=C(CH₃)-(CH₃)C=NAr*；Ar：2,6-二异丙基苯基；Ar*：2,6-二(4-叔丁基苯基)苯基（4b），2,6-二(4-OCH₃)-苯基）苯基（4c））被合成，并通过与（DME）NiBr₂反应转化为相应的镍二溴化合物（5b，c）。这些配合物在常温下通过与MAO处理被激活用于乙烯聚合。产生的高分子量聚合物产品（M_W > 4.0 x 10⁶ g mol^-1）具有支化微观结构（主要为甲基基团），如¹³C NMR光谱所示。通过适当选择2,6-二苯基修饰的苯胺基团可以控制支化程度，从而产生熔融转变范围在92 - 130 °C之间。
• Investigations into the preparation of groups 13–15 N-heterocyclic carbene analogues
  作者：Robert J. Baker、Cameron Jones、David P. Mills、Glesni A. Pierce、Mark Waugh

  DOI：10.1016/j.ica.2006.12.014

  日期：2008.1

  Attempts have been made to prepare a variety of groups 13 - 15 N-heterocyclic carbenoid systems. The work in group 13 led to two structurally characterized, paramagnetic gallium(III) heterocycles, [I2Ga[N(R)C(Me)](2)}], R = C6H3Pr2i-2, 6 (Ar) or C6H3(C6H4Bu'-4)(2)-2,6. Reduction of the former gave the anionic gallium(I) heterocyclic complex, [K(tmeda)][:Ga[N(Ar)C(Me)](2)}], which was oxidatively coupled, affording the structurally characterized digallane(4), [Ga[N(Ar)C(Me)](2)}](2). From group 14, the new germanium(IV) heterocycle, [Cl2Ge[N(Ar)C(H)](2)}], and the N-heterocyclic germylene, [:Ge[N(Ar)C(H)](2)}], have been prepared and fully characterized. Attempts to prepare N-heterocyclic silylene, phosphenium and arsenium compounds were unsuccessful and led instead to the silyl, phosphino and arsino-substituted ene-amines, [(ClnE)(2)mu-[N(Ar)C(H)](2)}], E = Si, n = 3; E = P or As, n = 2. (c) 2006 Elsevier B.V. All rights reserved.
• New Nickel(II) Diimine Complexes and the Control of Polyethylene Microstructure by Catalyst Design
  作者：Dieter Meinhard、Marcus Wegner、Georgy Kipiani、Andrew Hearley、Peter Reuter、Stefan Fischer、Othmar Marti、Bernhard Rieger

  DOI：10.1021/ja070224i

  日期：2007.7.1

  around the nickel(II) center that influence the polymer microstructure. At elevated reaction temperature and pressure, and in the presence of hydrogen, 2a-e catalyze the homopolymerization of ethylene to give branched PE products ranging from HD- to LLD-PE grades. The polymerization results indicate the possibility of precise microstructure control depending on the particular complex substitution. Preliminary

  以不同取代的硼酸作为通用构件，以简单、高产的路线合成了新的“邻芳基”α-二亚胺配体 ah。在二亚胺配体存在下，复合物前体二乙酰丙酮-镍 (II) 与三苯甲基盐（如 [CPh3] [B(C6F5)4] 或 [CPh3] [SbCl6]）的反应得到单阳离子方形平面复合物 2a -g 几乎是定量的产量。将合适的晶体 (2d',e,f,g) 提交给 X 射线衍射分析。开发了一种几何模型来描述影响聚合物微观结构的镍 (II) 中心周围配体碎片的取向。在升高的反应温度和压力下，在氢气存在下，2a-e 催化乙烯的均聚反应，得到从 HD- 到 LLD-PE 等级的支化 PE 产品。聚合结果表明根据特定的复杂取代进行精确微观结构控制的可能性。通过单轴拉伸对材料密度和机械性能的初步研究直至失效指向新的材料特性，该特性可由催化剂设计的简单乙烯单体产生。