bis(diisopropylphenyliminoethylpyridyl)vanadium(III) trichloride | 250163-87-2

• 英文名称: bis(diisopropylphenyliminoethylpyridyl)vanadium(III) trichloride
• 英文别名: [2,6-((2,6-ⁱPr₂C₆H₃)N=CMe)₂C₅H₃N]V^IIICl₃；2,6-[2,6-(i-Pr)2C6H5N=C(CH3)]2VCl3；VCl3(2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine)
• CAS: 250163-87-2
• 化学式: C₃₃H₄₃Cl₃N₃V
• 分子量: 639.025
• InChiKey: TUDCUQRIAARRIQ-VRCYMSAESA-K

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：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  bis(diisopropylphenyliminoethylpyridyl)vanadium(III) trichloride 在 NaH 作用下， 以 四氢呋喃 为溶剂， 以35%的产率得到[2,6-[2,6-(i-Pr)2C6H3N=C(CH3)]2(C5H3N)(THF)V]2(μ-N2)*hexane
  参考文献：
  名称：

  Dinitrogen Partial Reduction by Formally Zero- and Divalent Vanadium Complexes Supported by the Bis-iminopyridine System

  摘要：

  Reduction of the two trivalent 2,6-{[2,6-(i-Pr)(2)C6H5]N=C(CH3)](2)(C5H3N)VCl3 and [2,6-{[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]-VCI(THF) complexes with excess NaH afforded two corresponding end-on dinitrogen-bridged complexes [2,6-{[2,6-(i-Pr)(2)C6H5]N=C(CH3)}(2)(C5H3N)V](2)(m-N-2).(hexane) (1) and [{[2,6-{[2,6-(i-Pr)(2)C6H3)N-C=(CH2)}(2)(C5H3N)]V](2)(m-N-2).(hexane) (3). Despite their very close structural similarity, the two species have completely different natures. The first is paramagnetic and may be regarded as generated by the two-electron attack of two formally zerovalent vanadium moieties on the same N-2 unit. In the nearly diamagnetic 3 instead, the N2 unit has been reduced by two vanadium atoms, formally divalent. Structural analysis and DFT calculations have indicated that partial reduction of the bridging nitrogen occurred for both complexes while, in the case of 1, substantial metal-to-ligand electron transfer also occurs.

  DOI：

  10.1021/ic048358+
• 作为产物：
  描述：

  [VCl3(thf)3] 、 2,6-双[1-(2,6-二异丙苯亚氨基)乙基]吡啶 以 四氢呋喃 为溶剂， 生成 bis(diisopropylphenyliminoethylpyridyl)vanadium(III) trichloride
  参考文献：
  名称：

  Synthesis of α-diimine V(iii) complexes and their role as ethylene polymerisation catalysts

  摘要：

  两种新型α-二亚胺钒配合物， [PhNC(Me)–C(Me)NPh]V(THF)Cl3 (1) 和 {[2,6-(i-Pr)2Ph]NCH–CHN[2,6-(i-Pr)2Ph]}VCl3 (2) 是通过VCl3(THF)3与相应的α-二亚胺配体的配体交换反应合成的。配合物1的化学结构通过X射线晶体学确定，发现其由一个扭曲的八面体几何结构的钒原子构成，并且其配位的THF的氧原子、二亚胺配体的两个氮原子和一个氯原子位于同一平面内。配合物1和2通过FT-IR、1H NMR和元素分析进行表征，2被鉴定为THF游离的V(III)二亚胺配合物。在用MAO或AlEt2Cl活化后，初步探讨了1和2作为聚乙烯聚合催化剂的行为，并与在类似条件下的{2,6-bis[2,6-(i-Pr)2PhNC(Me)]2(C5H3N)}VCl3 (3)进行了比较。对1–3进行AlEt2Cl活化时，在-40°C观察到适度的聚合活性，而相应的MAO活化催化剂表现出较低的活性。在-40°C时，活性位点的摩尔浓度相当低（在总钒的5-12%范围内），这是由于配合物缓慢烷基化后V(III)催化剂还原为无活性V(II)物种所致。在50°C时，观察到1–3-AlEt2Cl催化剂的聚乙烯聚合活性增加，生产率值的趋势与金属中心的立体障碍相符合。1–3催化剂的二亚胺配体与AlEt2Cl的烷基化导致活性位点的失活，在聚合条件下仅部分活性，而1和2与MAO的反应则导致活性物种的快速降解。

  DOI：

  10.1039/b105931a
• 作为试剂：
  描述：

  三聚丙烯 在 bis(diisopropylphenyliminoethylpyridyl)vanadium(III) trichloride 作用下， 以 甲苯 为溶剂， 反应 1.0h， 生成 异己烯 、 反-4-甲基-2-戊烯 、 4-甲基-1-戊烯
  参考文献：
  名称：

  Homogeneous catalytic dimerization of propylene with bis(imino)pyridine vanadium(III) complexes

  摘要：

  A series of new bis(imino)pyridine vanadium(III) complexes was synthesized. They were tested for the homogeneous catalytic dimerization of propylene after activation with MAO. The activity and selectivity depend on the ligand structure of the corresponding organic coordination compound. The influence of PPh(3) as an additive was investigated and high dependency could be observed. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2010.02.013

文献信息

• Organometallic mediated radical polymerization of vinyl acetate using bis(imino)pyridine vanadium trichloride complexes
  作者：Mitchell R. Perry、Laura E. N. Allan、Andreas Decken、Michael P. Shaver

  DOI：10.1039/c3dt32625j

  日期：——

  trichloride complexes is described. The controlled radical polymerization activity towards vinyl acetate of these, and eight other bis(imino)pyridine vanadium trichloride complexes previously reported, is investigated. Those complexes possessing variation at the N-aryl para-position with no steric protection offered by ortho-substituents (4 examples) result in poor control over poly(vinyl acetate) polymerization

  描述了一种新型配体和六种新型三氯化钒（III）配合物的合成和表征。受控的自由基聚合活性醋酸乙烯酯在这些化合物中，还研究了先前报道的其他八种双（亚氨基）吡啶三氯化钒钒配合物。那些在N-芳基对位具有变化而没有由邻位取代基提供的空间保护的络合物（4个实施例）导致对聚（乙酸乙烯酯）聚合的控制较差。控制与在增加的空间体积改善邻的位上的Ñ-芳基取代基（4个例子），尽管试图增加空间体积超过异丙基是不成功的。当使用脂族取代基时，合成具有取代的亚胺主链的双（亚氨基）吡啶三氯化钒钒配合物可恢复聚合控制（4个实例），但不再对催化剂寿命产生任何大的改善。为了改善催化剂寿命，还研究了聚合条件的改变。单体范围扩大到包括其他乙烯基酯，特别是衍生自可再生资源的乙烯基酯，显示出令人鼓舞的结果。
• Immobilization and activation of 2,6-bis(imino)pyridyl Fe, Cr and V precatalysts using a MgCl2/AlRn(OEt)3−n support: Effects on polyethylene molecular weight and molecular weight distribution
  作者：Rubin Huang、Nileshkumar Kukalyekar、Cor E. Koning、John C. Chadwick

  DOI：10.1016/j.molcata.2006.07.030

  日期：2006.12

  Ethylene polymerizations carried out with various bis(imino)pyridyl iron, chromium and vanadium complexes immobilized on a MgCl2/AIR(n)(OEt)(3-n) support gave relatively broad polyethylene molecular weight distributions in the case of iron, but high molecular weight and a very narrow molecular weight distribution with vanadium, indicative of a single active species. The narrow MWD was confirmed by melt rheometry. Similar results were obtained after reaction of the bis(imino)pyridyl complex LVCl3 (6) with MeLi or AlEt3, where alkylation of the pyridine ring gives a complex L'VCl2 (7). In the case of chromium, a bimodal distribution was obtained, with evidence of incomplete catalyst immobilization. The polyethylene molecular weights obtained with the iron complexes were strongly dependent on the substiments in the bis(imino)pyridyl ligand, and were somewhat higher than have been obtained in homogeneous polymerization. In contrast, the molecular weights obtained with the bis(imino)pyridyl chromium and vanadium complexes were much higher that those previously obtained under homogeneous conditions. In all cases, the activities of the immobilized catalysts were higher than those found in homogeneous polymerization. (c) 2006 Elsevier B.V. All rights reserved.