bis([1,1':3',1''-terphenyl]-2'-yloxy)niobium(V) chloride | 116642-98-9

• 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: bis([1,1':3',1''-terphenyl]-2'-yloxy)niobium(V) chloride
• CAS: 116642-98-9
• 化学式: C₃₆H₂₆Cl₃NbO₂
• 分子量: 689.867
• InChiKey: ZKMVGDSDVHDSGL-UHFFFAOYSA-I

物化性质

• 闪点：
  151 °F

计算性质

• 辛醇/水分配系数(LogP)：
  11.79
• 重原子数：
  42.0
• 可旋转键数：
  8.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

安全信息

• 安全说明：
  S26,S36/37/39,S45,S53

反应信息

• 作为反应物：
  描述：

  bis([1,1':3',1''-terphenyl]-2'-yloxy)niobium(V) chloride 、 Mg(4-methylbenzyl)2 以 苯 为溶剂， 以48%的产率得到Nb(OC₆H₃(C₆H₅)2)2(CH₂C₆H₄CH₃)3
  参考文献：
  名称：

  Mechanistic study of the cyclometalation of o-arylphenoxide ligands at Group 5 metal centers

  摘要：

  A series of 4-methylbenzyl derivatives of niobium and tantalum of general formula M(OAr)2-(CH2C6H4-4-Me)3 (OAr = various 2,6-diaryl- or 2,4,6-triarylphenoxides) have been synthesized. Thermolysis of these compounds at temperatures ranging from 100 to 150-degrees-C is found to lead to the elimination of 1 equiv of p-xylene and formation of a series of cyclometalated compounds in which intramolecular activation of the aromatic CH bond of one of the substituent aryl rings of an aryl oxide ligand had taken place. A mechanistic investigation of the reactivity was carried by utilizing 2,4,6-triarylphenoxide groups in which the 2-aryl group contained the para substituent CH3, CH3O, and Cl. The product distribution of these competitive ring-closure reactions was estimated by using H-1 NMR spectroscopy. The effect of substituents within the aryl ring upon the rate of ring closure was found to be slight. It was found, however, that irrespective of whether an electron-donating (CH3) or electron-withdrawing (Cl) substituent was used the substituted ring underwent metalation preferentially over the nonsubstituted ring. The results of this study are inconsistent with these reactions following an electrophilic aromatic substitution pathway proceeding via an arenium ion intermediate being operative for these reactions. A structural study of the tris(4-methylbenzyl) substrates M(OC6H3Ph2-2,6)2(CH2C6H4Me)3 (M = Nb, Ta) showed the compounds to be isomorphous in the solid state with trans, axial aryl oxide ligands and three equatorial 4-methylbenzyl groups about the metal center. Crystal data at 22-degrees-C for Nb(OC6H3Ph2-2,6)2(CH2C6H4Me)3 are as follows: a = 13.008 (3) angstrom, b = 14.356 (3) angstrom, c = 15.235 (2) angstrom, alpha = 105.49 (1)-degrees, beta = 100.98 (1)-degrees, gamma = 91.46 (2)-degrees, Z = 2, d(calcd) = 1.227 g cm-3 in space group P1BAR. Crystal data for Ta(OC6H3Ph2-2,6)2(CH2C6H4Me)3 at 20-degrees-C are as follows: a = 12.982 (2) angstrom, b = 14.348 (2) angstrom, c = 15.210 (5) angstrom, alpha = 105.49 (2)-degrees, beta = 100.81 (2)-degrees, gamma = 01.36 (2)-degrees, Z = 2, d(calcd) = 1.341 g cm-3 in space group P1BAR. Both compounds contain one toluene solvate molecule per metal.

  DOI：

  10.1021/om00047a067
• 作为产物：
  描述：

  2,6-二苯基苯酚 、 五氯化铌 以 苯 为溶剂， 以94.4%的产率得到bis([1,1':3',1''-terphenyl]-2'-yloxy)niobium(V) chloride
  参考文献：
  名称：

  空间上拥挤的芳氧基配体的化学反应-VII。2,6-二苯酚的一些第4族和第5族金属衍生物的合成，结构和光谱性质

  摘要：

  已经合成了一系列含有辅助配体2，6-二苯酚（OAr-2，6Ph 2）的早期过渡金属有机金属衍生物。化学计量的化合物Ti（OAr-2,6Ph 2）2（R）2（R = CH 3，CH 2 SiMe 3，CH 2 Ph和Ph）和Ti（OAr-2,6Ph）3（R）（R =通过用所需量的苯酚HOAr-2,6Ph 2处理相应的均烷基烷基TiR 4来获得CH 3，CH 2 SiMe 3）。对于第5组金属Nb和Ta，甲基衍生物M（OAr-2,6Ph 2）2（CH 3）3和M（OAr-2,6Ph 2）3（CH 3）2通过相应的氯-芳基氧化物的甲基化获得。除了常规的光谱表征外，二苯基Ti（OAr-2,6Ph 2）2（Ph）2和单烷基Ti（OAr-2,6Ph 2）3（CH 2 SiMe 3X射线衍射技术已在结构上对其进行了表征。这两个分子都围绕钛原子包含一个伪四面体环境，其短的1.794（3）–1.806（2）

  DOI：

  10.1016/s0277-5387(00)84541-6