bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amine | 1226968-78-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amine
• 英文别名: di(2-(pyrazol-1-yl)-4-tolyl)amine；di(2-(pyrazolyl)-p-tolyl)amine；di(2-pyrazolyl-p-tolyl)amine；di(2-(pyrazol-1-yl)-p-tolyl)amine；H(MeMe)；4-methyl-N-(4-methyl-2-pyrazol-1-ylphenyl)-2-pyrazol-1-ylaniline
• CAS: 1226968-78-0
• 化学式: C₂₀H₁₉N₅
• 分子量: 329.404
• InChiKey: PPICQPRJBHQQBM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.1
• 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：

  五羰基溴铼(I) 、 bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amine 以 甲苯 为溶剂， 生成 fac-[Re(I)Br(CO)3(di(2-pyrazolyl-p-tolyl)amine-κ2N,N')]
  参考文献：
  名称：

  化学切换tricarbonylrhenium的行为（我）的新氧化还原活性“钳”配位体的配合物†

  摘要：

  三羰基hen（I）配合物的结构和光电性质。二（2-吡唑基-对甲苯基）胺 在中性和去质子化（单负） 酰胺基）的形式进行了调查。由于配体的非纯性质，配合物与布朗斯台德酸或碱的反应导致颜色和电化学活性发生明显变化。

  DOI：

  10.1039/c001344g
• 作为产物：
  描述：

  4,4'-二甲基二苯胺 在 copper(l) iodide 、 溴 、 potassium carbonate 、 N,N'-二甲基乙二胺 作用下， 以 甲醇 、 5,5-dimethyl-1,3-cyclohexadiene 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amine
  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

• Syntheses and Electronic Properties of Rhodium(III) Complexes Bearing a Redox-Active Ligand
  作者：Sarath Wanniarachchi、Brendan J. Liddle、Brandon Kizer、Jeewantha S. Hewage、Sergey V. Lindeman、James R. Gardinier

  DOI：10.1021/ic300772h

  日期：2012.10.15

  (NEt4)[(L)RhCl3]·H2O, 2·H2O. Complex 2·H2O reacts readily with excess pyridine, triethylphosphine, or pyrazine (pyz) to eliminate NEt4Cl and give charge-neutral complexes trans-(L)RhCl2(py), trans-3, trans-(L)RhCl2(PEt3), trans-4, or trans-(L)RhCl2(pyz), trans-5, where the incoming Lewis base is trans- to the amido nitrogen of the meridionally coordinating ligand. Heating solutions of complexes trans-3 or trans-4

  制备了一系列具有氧化还原活性的配体H（L =双（4-甲基-2-（1 H-吡唑-1-基）苯基）氨基的铑（III）配合物，并且其电子性质为研究过。因此，加热的商业的RhCl的乙醇溶液3 ·3H 2 O运用H（大号）导致不溶性的沉淀[H（大号）]的RhCl 3，1。[H（L）] RhCl 3的甲醇悬浮液与NEt 4 OH的反应引起配体去质子化，并提供接近定量的可溶性深绿色标题化合物（NEt 4）[（L）RhCl 3]·H 2 O，2 ·H 2 O.复杂2 ·H 2 ö发生反应容易地与过量的吡啶，三乙基膦，或吡嗪（PYZ），以消除净4 Cl和给予电荷中性的配合物的反式- （大号）的RhCl 2（ py），trans - 3，trans-（L）RhCl 2（PEt 3），trans - 4或trans-（L）RhCl 2（pyz），trans - 5，其中进入的Lewis碱反式转化为子午配位配体的酰胺氮。加热配合物的溶液的反式-
• Using sterics to promote reactivity in fac-Re(CO)3 complexes of some ‘non-innocent’ NNN-pincer ligands
  作者：Sarath Wanniarachchi、Brendan J. Liddle、John Toussaint、Sergey V. Lindeman、Brian Bennett、James R. Gardinier

  DOI：10.1039/c1dt10030k

  日期：——

  Two new redox active ligands based on di(2-(3-organopyrazolyl)-p-tolyl)amine have been prepared in order to investigate potential effects of steric bulk on the structures, electronic properties, or reactivity of tricarbonylrhenium(I) complexes. Replacing the hydrogens at the 3-pyrazolyl positions with alkyl groups causes significant distortion to the ligand framework due to potential interactions between these groups when bound to a fac-Re(CO)3 moiety. The distortions effectively increase the nucleophilic character of the central amino nitrogen and ligand-centered reactivity of the metal complexes.

  我们制备了两种基于二(2-(3-有机吡唑基)-p-甲苯基)胺的新型氧化还原活性配体，以研究立体结构对三羰基铼(I)配合物的结构、电子特性或反应活性的潜在影响。用烷基取代 3-吡唑位上的氢会导致配体框架发生显著变形，这是由于这些基团与面-Re(CO)3 分子结合时可能发生相互作用。这些变形有效地提高了中心氨基氮的亲核特性和金属配合物以配体为中心的反应活性。
• Electronic Communication Across Diamagnetic Metal Bridges: A Homoleptic Gallium(III) Complex of a Redox-Active Diarylamido-Based Ligand and Its Oxidized Derivatives
  作者：Brendan J. Liddle、Sarath Wanniarachchi、Jeewantha S. Hewage、Sergey V. Lindeman、Brian Bennett、James R. Gardinier

  DOI：10.1021/ic301437f

  日期：2012.12.3

  Complexes with cations of the type [Ga(L)2]n+ where L = bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amido and n = 1, 2, 3 have been prepared and structurally characterized. The electronic properties of each were probed by electrochemical and spectroscopic means and were interpreted with the aid of density functional theory (DFT) calculations. The dication, best described as [Ga(L–)(L0)]2+, is a Robin-Day

  [Ga(L) 2 ] n +型阳离子配合物，其中 L = 双(4-甲基-2-(1H-吡唑-1-基)苯基)酰胺和n = 1, 2, 3结构特征。每个的电子特性通过电化学和光谱手段探测，并在密度泛函理论 (DFT) 计算的帮助下进行解释。最好的描述为 [Ga(L – )(L 0 )] 2+ 的指示是 Robin-Day II 类混合价物质。因此，在 6390–6925 cm –1范围内的 NIR 光谱中发现了一个宽的、弱的、依赖于溶剂的间隔电荷转移 (IVCT) 带，取决于溶剂。能带形状分析以及 Hush 和 Marcus 关系的使用揭示了适度的电子耦合，H ab约为 200 cm –1，以及电子转移的大速率常数k et，在氧化还原活性之间的数量级为 10 10 s –1配体。二氧化配合物 [Ga(L 0 ) 2 ] 3+在其固态 X 带电子顺磁共振 (EPR) 光谱中在 5 K 处显示半场 Δ
• 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+).