cis,mer-Nb(NCMe3)Cl3(1,2-dimethoxyethane) | 189813-39-6

• 英文名称: cis,mer-Nb(NCMe3)Cl3(1,2-dimethoxyethane)
• 英文别名: [NbCl₃(NtBu)(dme)]
• CAS: 189813-39-6
• 化学式: C₈H₁₉Cl₃NNbO₂
• 分子量: 360.51
• InChiKey: DSCWTOHAQMLXKL-UHFFFAOYSA-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

• 作为产物：
  描述：

  乙二醇二甲醚 、 五氯化铌 、 叔丁胺 在 吡啶 、 zinc(II) chloride 作用下， 生成 cis,mer-Nb(NCMe3)Cl3(1,2-dimethoxyethane)
  参考文献：
  名称：

  活化的铌和钽亚胺络合物：从可调聚合到选择性乙烯二聚体系

  摘要：

  铌和钽亚氨基络合物[CpMCl 2（NDipp）]，[MCl 3（NR）（dme）]（R = t Bu，Ph，2,6 - i Pr 2 C 6 H 3（Dipp）和Mes） ，和[TaCl 3（NDipp）（tmeda）]与EtAlCl 2结合测试了乙烯的二聚作用。铌系统根据酰亚胺配体的性质提供了二聚体或聚合物，其总生产率在720至13,720（mol C 2 H 4）（mol Nb）-1范围内。产生的聚乙烯（LDPE或HDPE）的性质取决于亚胺基配体和进行催化的铌浓度。相比之下，钽/二甲醚体系均能介导乙烯二聚，生产率最高为4,503（mol C 2 H 4）（mol Ta）-1，对丁烯的总选择性为73-81 wt％。在二聚体馏分中对1-丁烯的选择性在72％至100％的范围内。[TaCl 3（NDipp）（tmeda）]的生产率比含dme的同类产品高六倍，但以对1-丁烯的选择性为代价。对于

  DOI：

  10.1002/cctc.201801849

文献信息

• A General Route to Labile Niobium and Tantalum d⁰ Monoimides. Discussion of Metal−Nitrogen Vibrational Modes
  作者：Andrey V. Korolev、Arnold L. Rheingold、Darryl S. Williams

  DOI：10.1021/ic961360j

  日期：1997.6.1

  Reaction of TaCl5 with 2 equiv of an amine in the presence of sodium silicate and pyridine affords Ta(NR)Cl-3(py)(2) in good yield. Reaction of NbCl5 with ZnCl2 followed by addition of an amine RNH2 and pyridine affords M(NR)Cl-3(dme) (dme is 1,2-dimethoxyethane). For niobium this reaction proceeds smoothly regardless of the amine but is ineffective with tantalum and alkylamines. An alternative route involves reaction of TaCl5 with 3 equiv of RNH2 to form [RNH3](2)[Ta(NR)Cl-5], followed by reaction of this salt with ZnCl2 in the presence of dme. The molecular structure of Nb((NBu)-Bu-t)Cl-3(dme) (formula C8H19Cl3NNbO2) was determined by X-ray crystallography (monoclinic space group Cc with a 30.565(4) Angstrom, b = 7.2406(13) Angstrom, c = 13.915(2) Angstrom, beta = 90.626(7)degrees, V = 3079.4(8) Angstrom(3), Z = 8). The Nb-N bond length is 1.72 Angstrom with a Nb-N-C bond angle of 177 degrees in a distorted octahedral structure. In order to characterize the M-N stretching frequencies in these compounds, IR data for each compound are compared with calculated stretching frequencies using the commercially available Spartan calculation package. These experiments reveal that there is no real M-N stretching frequency in these imidos. Rather, the M-N modes are strongly coupled to N-C and C-H or C-C modes in these imidos. LR active modes are observed at similar to 1260 cm(-1) for tantalum alkyl imidos and similar to 1350 cm(-1) for tantalum aryl imidos. These correspond to a Ta-(N-C) stretch coupled to the CR3 umbrella deformation.