N-(4-methyl-2-(1H-pyrazol-1-yl)phenyl)-2-(1H-pyrazol-1-yl)benzenamine | 1345047-53-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: N-(4-methyl-2-(1H-pyrazol-1-yl)phenyl)-2-(1H-pyrazol-1-yl)benzenamine
• 英文别名: H(MeH)；4-methyl-2-pyrazol-1-yl-N-(2-pyrazol-1-ylphenyl)aniline
• CAS: 1345047-53-1
• 化学式: C₁₉H₁₇N₅
• 分子量: 315.377
• InChiKey: XAONAFJLDXWUEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  47.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(4-methyl-2-(1H-pyrazol-1-yl)phenyl)-2-(1H-pyrazol-1-yl)benzenamine 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 2.67h， 生成 (4-Bromo-2-pyrazol-1-ylphenyl)-(4-methyl-2-pyrazol-1-ylphenyl)azanide;nickel(2+)
  参考文献：
  名称：

  Homoleptic Nickel(II) Complexes of Redox-Tunable Pincer-type Ligands

  摘要：

  Different synthetic methods have been developed to prepare eight new redox-active pincer-type ligands, H(X,Y), that have pyrazol-1-yl flanking donors attached to an ortho-position of each ring of a diarylamine anchor and that have different groups, X and Y, at the para-aryl positions. Together with four previously known H(X,Y) ligands, a series of 12 Ni(X,Y)(2) complexes were prepared in high yields by a simple one-pot reaction. Six of the 12 derivatives were characterized by single-crystal X-ray diffraction, which showed tetragonally distorted hexacoordinate nickel(II) centers. The nickel(II) complexes exhibit two quasi-reversible one-electron oxidation waves in their cyclic voltammograms, with half-wave potentials that varied over a remarkable 700 mV range with the average of the Hammett sigma(p) parameters of the para-aryl X, Y groups. The one- and two-electron oxidized derivatives [Ni(Me,Me)(2)](BF4)(n) (n = 1, 2) were prepared synthetically, were characterized by X-band EPR, electronic spectroscopy, and single-crystal X-ray diffraction (for n = 2), and were studied computationally by DFT methods. The dioxidized complex, [Ni(Me,Me)(2)] (BF4)(2), is an S = 2 species, with nickel(II) bound to two ligand radicals. The mono-oxidized complex [Ni(Me,Me)(2)](BF4), prepared by comproportionation, is best described as nickel(II) with one ligand centered radical. Neither the mono- nor the dioxidized derivative shows any substantial electronic coupling between the metal and their bound ligand radicals because of the orthogonal nature of their magnetic orbitals. On the other hand, weak electronic communication occurs between ligands in the mono-oxidized complex as evident from the intervalence charge transfer (IVCT) transition found in the near-IR absorption spectrum. Band shape analysis of the IVCT transition allowed comparisons of the strength of the electronic interaction with that in the related, previously known, Robin-Day class II mixed valence complex, [Ga(Me,Me)(2)](2+).

  DOI：

  10.1021/ic500657e
• 作为产物：
  描述：

  2-溴-4-甲基苯胺 在 copper(l) iodide 、 caesium carbonate 作用下， 以 1,4-二氧六环 、 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 生成 N-(4-methyl-2-(1H-pyrazol-1-yl)phenyl)-2-(1H-pyrazol-1-yl)benzenamine
  参考文献：
  名称：

  二（2-吡唑基芳基）酰胺基-钳位配体的羰基铑（I）配合物的制备，性质和反应活性

  摘要：

  一系列六个羰基铑（I）配合物，分别是三个新的和三个先前报道的二（2-3R-吡唑基）-对-Z / X-芳基）酰胺钳式配体，（R ZX）Rh（CO），（R是替代在3-吡唑基位置邻近该金属; Z和X与芳基取代基对位-对芳基酰氨基氮）中制备。对金属络合物进行了研究，以评估如何通过改变沿配体周边的基团以及如何将其与其他已知的羰基铑（I）钳形衍生物进行比较来调节其性质和反应性。发现2-（吡唑基）-4-X-苯胺（X = Me或CF 3）与2-bromoaryl-1 H之间新的CuI催化的偶联反应促进了这项研究-吡唑，可以制造带有两个不同芳基臂的钳形配体。NNN钳式支架为羰基铑（I）片段提供了一个富电子的环境，如羰基拉伸频率在1948–1968 cm -1范围内所示。这样，在室温下的丙酮溶液中，与碘甲烷的氧化加成（OA）反应即刻进行，形成反式（NNN-钳子）Rh（Me）（CO）（I）。与碘乙烷的OA反应在

  DOI：

  10.1016/j.jorganchem.2011.08.013

文献信息

• Preparation, properties, and reactivity of carbonylrhodium(I) complexes of di(2-pyrazolylaryl)amido-pincer ligands
  作者：Sarath Wanniarachchi、Brendan J. Liddle、Sergey V. Lindeman、James R. Gardinier

  DOI：10.1016/j.jorganchem.2011.08.013

  日期：2011.11

  six carbonylrhodium(I) complexes of three new and three previously reported di(2-3R-pyrazolyl)-p-Z/X-aryl)amido pincer ligands, (RZX)Rh(CO), (R is the substituent at the 3-pyrazolyl position proximal to the metal; Z and X are the aryl substituents para- to the arylamido nitrogen) were prepared. The metal complexes were studied to assess how their properties and reactivities can be tuned by varying

  一系列六个羰基铑（I）配合物，分别是三个新的和三个先前报道的二（2-3R-吡唑基）-对-Z / X-芳基）酰胺钳式配体，（R ZX）Rh（CO），（R是替代在3-吡唑基位置邻近该金属; Z和X与芳基取代基对位-对芳基酰氨基氮）中制备。对金属络合物进行了研究，以评估如何通过改变沿配体周边的基团以及如何将其与其他已知的羰基铑（I）钳形衍生物进行比较来调节其性质和反应性。发现2-（吡唑基）-4-X-苯胺（X = Me或CF 3）与2-bromoaryl-1 H之间新的CuI催化的偶联反应促进了这项研究-吡唑，可以制造带有两个不同芳基臂的钳形配体。NNN钳式支架为羰基铑（I）片段提供了一个富电子的环境，如羰基拉伸频率在1948–1968 cm -1范围内所示。这样，在室温下的丙酮溶液中，与碘甲烷的氧化加成（OA）反应即刻进行，形成反式（NNN-钳子）Rh（Me）（CO）（I）。与碘乙烷的OA反应在
• Homoleptic Nickel(II) Complexes of Redox-Tunable Pincer-type Ligands
  作者：Jeewantha S. Hewage、Sarath Wanniarachchi、Tyler J. Morin、Brendan J. Liddle、Megan Banaszynski、Sergey V. Lindeman、Brian Bennett、James R. Gardinier

  DOI：10.1021/ic500657e

  日期：2014.10.6

  Different synthetic methods have been developed to prepare eight new redox-active pincer-type ligands, H(X,Y), that have pyrazol-1-yl flanking donors attached to an ortho-position of each ring of a diarylamine anchor and that have different groups, X and Y, at the para-aryl positions. Together with four previously known H(X,Y) ligands, a series of 12 Ni(X,Y)(2) complexes were prepared in high yields by a simple one-pot reaction. Six of the 12 derivatives were characterized by single-crystal X-ray diffraction, which showed tetragonally distorted hexacoordinate nickel(II) centers. The nickel(II) complexes exhibit two quasi-reversible one-electron oxidation waves in their cyclic voltammograms, with half-wave potentials that varied over a remarkable 700 mV range with the average of the Hammett sigma(p) parameters of the para-aryl X, Y groups. The one- and two-electron oxidized derivatives [Ni(Me,Me)(2)](BF4)(n) (n = 1, 2) were prepared synthetically, were characterized by X-band EPR, electronic spectroscopy, and single-crystal X-ray diffraction (for n = 2), and were studied computationally by DFT methods. The dioxidized complex, [Ni(Me,Me)(2)] (BF4)(2), is an S = 2 species, with nickel(II) bound to two ligand radicals. The mono-oxidized complex [Ni(Me,Me)(2)](BF4), prepared by comproportionation, is best described as nickel(II) with one ligand centered radical. Neither the mono- nor the dioxidized derivative shows any substantial electronic coupling between the metal and their bound ligand radicals because of the orthogonal nature of their magnetic orbitals. On the other hand, weak electronic communication occurs between ligands in the mono-oxidized complex as evident from the intervalence charge transfer (IVCT) transition found in the near-IR absorption spectrum. Band shape analysis of the IVCT transition allowed comparisons of the strength of the electronic interaction with that in the related, previously known, Robin-Day class II mixed valence complex, [Ga(Me,Me)(2)](2+).