(2-(2,4,6-iPr3C6H2)C6H4)2N3H | 909121-88-6

• 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: (2-(2,4,6-iPr3C6H2)C6H4)2N3H
• 英文别名: [2-(2,4,6-iPr3C6H2)C6H4]NNNH[2-(2,4,6-iPr3C6H2)C6H4]；N3H(C6H4(2,4,6-C6H2iPr3))2；2-[2,4,6-tri(propan-2-yl)phenyl]-N-[[2-[2,4,6-tri(propan-2-yl)phenyl]phenyl]diazenyl]aniline
• CAS: 909121-88-6
• 化学式: C₄₂H₅₅N₃
• 分子量: 601.919
• InChiKey: UPAIMJXBMQUYGY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14
• 重原子数：
  45
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  36.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2-(2,4,6-iPr3C6H2)C6H4)2N3H 、 thallium (I) ethoxide 以 正庚烷 、 甲苯 为溶剂， 以77%的产率得到TlN3(2-(2,4,6-iPr3C6H2)C6H4)2
  参考文献：
  名称：

  Isostructural Potassium and Thallium Salts of Sterically Crowded Triazenes: A Structural and Computational Study

  摘要：

  Because of their similar cationic radii, potassium and thallium(l) compounds are usually regarded as closely related. Homologous molecular species containing either K+ or Tl+ are very rare, however. We have synthesized potassium and thallium salts MN3RR' derived from the biphenyl- or terphenyl-substituted triazenes Tph(2)N(3)H (1a), Dmp(Mph)N3H (1b), Dmp(Tph)N3H (1c), and (Me(4)Ter)(2)N3H (1d) (Dmp = 2,6-Mes(2)C(6)H(3) with Mes = 2,4,6-Me3C6H2; Me(4)Ter = 2,6-(3,5-Me2C6H3)(2)C6H3; Mph = 2-MesC(6)H(4); Tph = 2-TriPC(6)H(4) with Trip = 2,4,6-(Pr3C6H2)-Pr-i). The potassium complexes 2a-d were obtained in almost quantitative yield from the reaction of 1a-d with potassium metal in n-heptane. Metalation of 1a-d with TIOEt afforded the thallium triazenides 3a-d in high yields. All new compounds have been characterized by H-1 and C-13 NMR spectroscopy, elemental analysis, and X-ray crystallography and for selected species by melting point (not 3b), IR spectroscopy (2a, 2d, 3a, 3c, 3d), and mass spectrometry (2a, 3c). In the solid-state structures of monomeric 2a and 3a, quasi-monomeric 2b, 3b, 2c, and 3c, and dimeric 2d and 3d additional metal-eta(n)-pi-arene-interactions to the flanking arms of the biphenyl- and terphenyl groups in the triazenide ligands of decreasing hapticity n are observed. Remarkably, all homologous potassium and thallium complexes crystallize in isomorphous cells. For 2a and 3a, the nature of the M-N and M center dot center dot center dot C(arene) bonding was studied by density functional theory calculations.

  DOI：

  10.1021/ic800029z

文献信息

• Rare-earth metal bis(tetramethylaluminate) complexes supported by a sterically crowded triazenido ligand
  作者：Rannveig Litlabø、Hyui Sul Lee、Mark Niemeyer、Karl W. Törnroos、Reiner Anwander

  DOI：10.1039/b925837j

  日期：——

  Complexes [NNN]Ln(AlMe4)2 (Ln = Y, La, Nd, Lu) bearing the sterically demanding aryl-substituted triazenido ligand [(Tph)2N3] (Tph = [2-(2,4,6-iPr3C6H2)C6H4]) can be obtained from homoleptic complexes Ln(AlMe4)3 in moderate yields, both via protonolysis with [(Tph)2N3]H and a salt metathesis reaction pathway utilizing [(Tph)2N3]K. In the solid state the Y and Lu derivatives are isostructural, with both tetramethylaluminate groups coordinated in an η2 fashion, while one of the [AlMe4] ligands of the Nd derivative features a distorted η2 coordination mode. Due to the high affinity of the triazenido ligand toward the more Lewis-acidic and harder aluminium cation compared to the softer rare-earth metal centres, ligand redistribution is observed in solution and formation of byproduct [(Tph)2N3]AlMe2 is prominent. While the monoanionic triazenido ligand coordinates the rare-earth metal centres in an asymmetrical syn/anti fashion, it adopts an almost symmetric syn/syn configuration in the aluminium complex. Attempts were also made to produce putative dimethyl complexes [(Tph)2N3]LnMe2} (Ln = Y, Lu) via cleavage of the aluminate moieties with diethyl ether. Furthermore, the intrinsic redistribution reactions are proposed to affect the performance of complexes [(Tph)2N3]Ln(AlMe4)2 in isoprene polymerization.

  络合物 [NNN]Ln(AlMe4)2（Ln = Y、La、Nd、Lu）含有立体要求较高的芳基取代的三嗪基配体 [(Tph)2N3] （Tph = [2-(2,4、Tph=[2-(2,4,6-iPr3C6H2)C6H4])，可以通过与[(Tph)2N3]H 的质子分解反应和利用[(Tph)2N3]K 的盐偏合成反应途径，从同质络合物 Ln(AlMe4)3 中以中等产率获得。在固态下，Y 和 Lu 衍生物的结构相同，两个四甲基铝酸盐基团都以η2 方式配位，而 Nd 衍生物的一个 [AlMe4] 配体具有扭曲的η2 配位模式。与较软的稀土金属中心相比，三氮杂环配体对路易斯酸性更强、更硬的铝阳离子具有较高的亲和力，因此在溶液中可以观察到配体的重新分布，副产物[(Tph)2N3]AlMe2 的形成也很明显。单阴离子三氮杂环配体以不对称的同步/反同步方式配位稀土金属中心，而在铝络合物中则采用几乎对称的同步/同步构型。研究人员还尝试用二乙醚裂解铝酸盐分子，从而制备出假定的二甲基配合物[(Tph)2N3]LnMe2}（Ln = Y、Lu）。此外，还提出了内在的再分布反应会影响络合物 [(Tph)2N3]Ln(AlMe4)2在异戊二烯聚合中的性能。
• Sterically crowded triazenides as novel ancillary ligands in copper chemistry
  作者：Hyui Sul Lee、Mark Niemeyer

  DOI：10.1016/j.ica.2011.01.079

  日期：2011.8

  We have synthesized copper salts MN3RR ' derived from the biphenyl-or m-terphenyl-substituted triazenes Tph(2)N(3)H (1a) and Dmp(Tph)N3H (1b) (Dmp = 2,6-Mes(2)C(6)H(3) with Mes = 2,4,6-Me3C6H2; Tph = 2TripC(6)H(4) with Trip = 2,4,6-i-Pr3C6H2). The homoleptic copper triazenide [CuN(3)Tph(2)] (2a) was obtained in high yield from the metallation of 1a with mesityl copper in n-heptane, while the complex [CuN3(Dmp)Tph] (2b) was generated by the same method in situ only. Reaction of 2a with triphenylphosphane gave the 2:1 adduct [CuN(3)Tph(2)(PPh3)(2)] (3a), regardless of the used complex/ donor ratio, while reaction of 2a or 2b with a stochiometric amount of t-butylisonitrile afforded the 1:1 adducts [Tph(2)N(3)CuCNtBu] (4a) and [Dmp(Tph) N(3)CuCNtBu] (4b). All new compounds (except 2b) have been characterized by H-1 NMR, C-13 NMR and IR spectroscopy, elemental analysis, melting point (not 2a), and X-ray crystallography. The IR spectroscopic examination of the v(C N) stretch in the isonitrile adducts 4a and 4b revealed the weaker donor character of the supporting triazenido ligands compared to related beta-diketiminato ligands. (C) 2011 Elsevier B.V. All rights reserved.
• Isostructural Potassium and Thallium Salts of Sterically Crowded Triazenes: A Structural and Computational Study
  作者：Hyui Sul Lee、Sven-Oliver Hauber、Denis Vinduš、Mark Niemeyer

  DOI：10.1021/ic800029z

  日期：2008.5.19

  Because of their similar cationic radii, potassium and thallium(l) compounds are usually regarded as closely related. Homologous molecular species containing either K+ or Tl+ are very rare, however. We have synthesized potassium and thallium salts MN3RR' derived from the biphenyl- or terphenyl-substituted triazenes Tph(2)N(3)H (1a), Dmp(Mph)N3H (1b), Dmp(Tph)N3H (1c), and (Me(4)Ter)(2)N3H (1d) (Dmp = 2,6-Mes(2)C(6)H(3) with Mes = 2,4,6-Me3C6H2; Me(4)Ter = 2,6-(3,5-Me2C6H3)(2)C6H3; Mph = 2-MesC(6)H(4); Tph = 2-TriPC(6)H(4) with Trip = 2,4,6-(Pr3C6H2)-Pr-i). The potassium complexes 2a-d were obtained in almost quantitative yield from the reaction of 1a-d with potassium metal in n-heptane. Metalation of 1a-d with TIOEt afforded the thallium triazenides 3a-d in high yields. All new compounds have been characterized by H-1 and C-13 NMR spectroscopy, elemental analysis, and X-ray crystallography and for selected species by melting point (not 3b), IR spectroscopy (2a, 2d, 3a, 3c, 3d), and mass spectrometry (2a, 3c). In the solid-state structures of monomeric 2a and 3a, quasi-monomeric 2b, 3b, 2c, and 3c, and dimeric 2d and 3d additional metal-eta(n)-pi-arene-interactions to the flanking arms of the biphenyl- and terphenyl groups in the triazenide ligands of decreasing hapticity n are observed. Remarkably, all homologous potassium and thallium complexes crystallize in isomorphous cells. For 2a and 3a, the nature of the M-N and M center dot center dot center dot C(arene) bonding was studied by density functional theory calculations.