[NbCl₃(NPh)(dme)] | 189813-47-6

• 英文名称: [NbCl₃(NPh)(dme)]
• 英文别名: cis,mer-Nb(NPh)Cl3(1,2-dimethoxyethane)；mer-(dimethoxyethane)Cl3Nb=NPh
• CAS: 189813-47-6
• 化学式: C₁₀H₁₅Cl₃NNbO₂
• 分子量: 380.5
• InChiKey: MKVKMKZOUSVFOS-UHFFFAOYSA-K

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：

  (三甲基硅基)甲基氯化镁 、 [NbCl₃(NPh)(dme)] 以 正己烷 为溶剂， 以>99 %的产率得到Nb(NC₆H₅)(CH₂SiMe₃)₃
  参考文献：
  名称：

  (Arylimido)niobium(V)–Alkylidenes 作为催化剂用于环烯烃的开环复分解聚合 (ROMP)：Nb(CHSiMe3)(NC6H5)[OC(CF3)3](PMe3)2 对环辛烯的 Z 特异性 ROMP

  摘要：

  (Arylimido)niobium(V)–alkylidene complexes, Nb(CHSiMe 3 )(NAr)[OC(CF 3 ) 3 ](PMe 3 ) 2 (Ar = C 6 H 5 ( 4 ), 2,6-F 2 C 6 H 3 , C 6 F 5 ( 6 ), Nb(CHSiMe 3 )(N-2,6-Cl 2 C 6 H 3 )(OC 6 F 5 )(PMe 3 ) 2 ( 7 ), Nb( CHSiMe 3 )(N-2,6-F 2 C6 H 3 )(OC 6 Cl 5 )(PMe 3 ) 2，已被制备和鉴定。五氟苯基亚氨基类似物6和7对降冰片烯的开环复分解聚合 (ROMP) 表现出优异的催化活性（TOF = 56.1, 53.7 s –1，分别在 25 °C 时）并且活性在 50 °C 时增加（TOF ≥ 352 秒–1）。制备的亚烷基催化顺式环辛烯（COE）的ROMP

  DOI：

  10.1021/acs.organomet.2c00665
• 作为产物：
  描述：

  乙二醇二甲醚 、 五氯化铌 、 苯胺 在 吡啶 、 zinc(II) chloride 作用下， 生成 [NbCl₃(NPh)(dme)]
  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

• Mono-anionic acetophenone imine ligands: synthesis, ortho-lithiation and first examples of group (v) metal complexes
  作者：Abdollah Neshat、Cheryl L. Seambos、John F. Beck、Joseph A. R. Schmidt

  DOI：10.1039/b903836a

  日期：——

  A series of niobium and tantalum imido complexes with mono-anionic ortho-metallated acetophenone imine ligands have been prepared and characterized using NMR spectroscopy, mass spectrometry and elemental analysis. These low symmetry complexes are produced with only one or two structural isomers in all cases and display interesting correlations between the steric bulk of the ligands employed and the isomers formed. Crystal structures of several new niobium and tantalum complexes are presented as confirmation of the connectivity in these structural isomers.

  我们利用核磁共振光谱法、质谱法和元素分析法制备了一系列具有单阴离子正交金属化苯乙酮亚胺配体的铌和钽亚胺配合物，并对其进行了表征。这些低对称性配合物在所有情况下都只有一种或两种结构异构体，并显示出配体的立体结构与所形成的异构体之间有趣的相关性。本文还展示了几种新的铌和钽配合物的晶体结构，以证实这些结构异构体之间的关联性。
• 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.