2,6-bis[(2,6-dimethylphenylimino)methyl]pyridine | 221391-10-2

• 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: 2,6-bis[(2,6-dimethylphenylimino)methyl]pyridine
• 英文别名: 2,6-diformylpyridinebis(2,6-dimethylamil)；N-(2,6-dimethylphenyl)-1-[6-[(2,6-dimethylphenyl)iminomethyl]pyridin-2-yl]methanimine
• CAS: 221391-10-2
• 化学式: C₂₃H₂₃N₃
• 分子量: 341.456
• InChiKey: MPWJFYLTJNZBFQ-UHFFFAOYSA-N

物化性质

• 沸点：
  519.2±50.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  37.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,6-bis[(2,6-dimethylphenylimino)methyl]pyridine 、 cadmium(II) chloride 以 正丁醇 为溶剂， 以91%的产率得到(2,6-bis[(2,6-dimethylphenylimino)methyl]pyridine)CdCl2
  参考文献：
  名称：

  Mixed-ligand complexes of cadmium(II) containing bulky polydentate nitrogen-based ligands

  摘要：

  The reaction of equimolar amounts of CdCl2, Tl[H2B(3-Bu(1)pz)(2)] (pz = pyrazolyl ring) and Na[Et2NCS2] yields [H2B(3-Bu(1)pz)(2)]Cd(S2CNEt2) (1) and a similar reaction using Tl[HB(3-Bu(1)pz)(3)] yields [HB(3-Bu(1)pz)(3)]Cd(S2CNEt2) (2). The solid state structure of [HB(3-Bu(1)pz)(3)]Cd(S2CNEt2) shows the arrangement of the donor atoms is a distorted trigonal bipyramid, an unusual geometry for a molecule containing a tridentate [HB(3-Bu(1)pz)(3)](-) ligand. Mixing CdCl2 with 2 equiv. of MeLi yields the Me2Cd intermediate that reacts with Tl[HB(3-Phpz)(3)] to yield [HB(3-Phpz)(3)]CdCH3 (3). Compound 3 reacts with thiotoluene to yield [HB(3-Phpz)(3)]CdS(p-C6H4CH3) (4) and mercaptopyridine to yield [HB(3-Phpz)(3)]Cd(SNC6H4) (5). The neutral 2,6-bis(2,6-dimethylphenylimino)pyridine ligand (pydim) reacts with CdCl2 in equimolar amounts to yield the adduct (pydim)CdCl2 (6). The cadmium(II) is in a five-coordinate arrangement that is best described as a distorted trigonal bipyramid. The three nitrogen atoms of the planar pyridine ligand occupy an equatorial and both axial sites, but the intrinsic bite angle of the ligand forces a significant distortion in the axial bond angle. Compound 6 reacts with an equimolar amount of Na[Et2NCS2] to yield [(pydim)Cd(S2CNEt2)][Cl] (7). The reaction of equimolar amounts of pydimMe(2) and Cd(NO3)(2) yields (pydimMe(2))Cd(NO3)(2) (8). In the structure of this complex, one nitrate ligand is bidentate and the other monodentate. If the bidentate ligand is considered as occupying one site of a polyhedron, the structure of 8 can be considered as a trigonal bipyramid, very similar to that of 6. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)00735-1
• 作为产物：
  描述：

  吡啶-2,6-二甲醛 、 2,6-二甲基苯胺 以 乙醇 为溶剂， 以86.8 %的产率得到2,6-bis[(2,6-dimethylphenylimino)methyl]pyridine
  参考文献：
  名称：

  带有芳香双醛亚胺 N^N^N 钳形配体的钯配合物；作为二氧化碳氢化催化剂的活性

  摘要：

  CO 2加氢可以作为使用CO 2作为C1碳源的途径，同时作为氢“储存”的手段。在此我们报告了新的吡啶-2,6-双(亚甲基)双(CH = NR)-氯化钯络合物的合成是(R = Ph, p -Br- C 6 H 4 , 2,6-二甲基-C 6 3 ）。所有配合物均通过1 H NMR、13充分表征C NMR、FT-IR、元素分析、质谱和单晶 X 射线衍射研究（如适用）。这项工作旨在调查和讨论取代基在电子效应、钳形配体系统主链的选择和取代基的空间效应方面的作用及其对 CO 2 加氢的作用。这些钳形配合物作为 CO 2氢化催化剂进行了研究，发现在直接催化二氧化碳氢化生成甲酸盐中非常有效，最高 TON 为 520。

  DOI：

  10.1016/j.poly.2023.116360

文献信息

• Novel olefin polymerization catalysts based on iron and cobalt
  作者：George J. P. Britovsek、Vernon C. Gibson、Stuart J. McTavish、Gregory A. Solan、Andrew J. P. White、David J. Williams、George J. P. Britovsek、Brian S. Kimberley、Peter J. Maddox

  DOI：10.1039/a801933i

  日期：——

  A new family of olefin polymerization catalysts, derived from iron and cobalt complexes bearing 2,6-bis(imino)pyridyl ligands, is described.

  一种基于含2,6-双(亚胺基)吡啶配体的铁和钴络合物的新型烯烃聚合催化剂系列被报道。
• Iron and Cobalt Ethylene Polymerization Catalysts Bearing 2,6-Bis(Imino)Pyridyl Ligands:  Synthesis, Structures, and Polymerization Studies
  作者：George J. P. Britovsek、Michael Bruce、Vernon C. Gibson、Brian S. Kimberley、Peter J. Maddox、Sergio Mastroianni、Stuart J. McTavish、Carl Redshaw、Gregory A. Solan、Staffan Strömberg、Andrew J. P. White、David J. Williams

  DOI：10.1021/ja990449w

  日期：1999.9.1

  The synthesis, characterization, and ethylene polymerization behavior of a series of iron and cobalt halide complexes, LMXn (M = Fe, X = Cl, n = 2, 3, X = Br, n = 2; M = Co, X = Cl, n = 2), bearing chelating 2,6-bis(imino)pyridyl ligands L [L = 2,6-(ArNCR1)2C5H3N] is reported. X-ray diffraction studies show the geometry at the metal centers to be either distorted square pyramidal or distorted trigonal

  一系列铁和钴卤化物配合物的合成、表征和乙烯聚合行为，LMXn (M = Fe, X = Cl, n = 2, 3, X = Br, n = 2; M = Co, X = Cl , n = 2)，据报道带有螯合 2,6-双（亚氨基）吡啶基配体 L [L = 2,6-(ArNCR1)2C5H3N]。X 射线衍射研究表明金属中心的几何形状是扭曲的四角锥体或扭曲的三角双锥体。用甲基铝氧烷 (MAO) 处理配合物 LMXn 导致高活性乙烯聚合催化剂将乙烯转化为高线性聚乙烯 (PE)。具有酮亚胺配体 (R1 = Me) 的 LFeX2 预催化剂比具有醛亚胺配体 (R1 = H) 的预催化剂活性高大约一个数量级。观察到 Fe 基酮亚胺催化剂的催化剂生产率在 3750-20600 g/mmol·h·bar 范围内，而 Co ketimine 系统的活性为 450-1740 g/mmol·h·bar。生产的聚合物的分子量
• Syntheses and structures of mono-thiocyanate complexes of cadmium(II) and lead(II) containing bulky nitrogen based polydentate ligands
  作者：Daniel L Reger、Terri D Wright、Mark D Smith、Arnold L Rheingold、Scott Kassel、Thomas Concolino、Brian Rhagitan

  DOI：10.1016/s0277-5387(02)01058-6

  日期：2002.8

  The solid state structure shows that the sterically demanding 3-tert-butyl groups enforce the formation of a tetrahedral, monomeric complex, the first four-coordinate cadmium(II)-thiocyanate complex to be structurally characterized. The decomposition of this compound produced [(ButHpz)2Cd(NCS)2]n (2) as shown by X-ray crystallography. It was not possible to form a lead(II) complex analogous to 1, but

  [Cd 2（thf）5 ]（BF 4）4与两个当量的反应。Tl [HB（3-Bu t pz）3 ]（pz =吡唑基环）的中间体产生中间体[[HB（3-Bu t pz 3 ] Cd} [BF 4 ]与硫氰酸钾反应生成[HB（3 -Bu t pz）3 ] Cd（NCS）（1）。固态结构表明，空间上需要的3-叔丁基会强制形成四面体单体配合物，即第一个四坐标的镉（II）-硫氰酸盐配合物的结构特征。该化合物的分解产生了[（Bu tX射线晶体学显示为Hpz）2 Cd（NCS）2 ] n（2）。不可能形成类似于1的Lead（II）络合物，但是使用较少空间要求的配体可以制备[HB（3,5-Me 2 pz）3 ] Pb（μ-NCS）} 2（3）和[HB（pz）3 ] Pb（μ-NCS）} n（4）。前者具有与两个μ-NCS-的二聚体结构小号，Ñ和μ-NCS-小号，š桥接SCN -配体，后者具有无限的2-
• Mixed-ligand complexes of cadmium(II) containing bulky polydentate nitrogen-based ligands
  作者：Daniel L. Reger、Terri D. Wright、Mark D. Smith

  DOI：10.1016/s0020-1693(02)00735-1

  日期：2002.5

  The reaction of equimolar amounts of CdCl2, Tl[H2B(3-Bu(1)pz)(2)] (pz = pyrazolyl ring) and Na[Et2NCS2] yields [H2B(3-Bu(1)pz)(2)]Cd(S2CNEt2) (1) and a similar reaction using Tl[HB(3-Bu(1)pz)(3)] yields [HB(3-Bu(1)pz)(3)]Cd(S2CNEt2) (2). The solid state structure of [HB(3-Bu(1)pz)(3)]Cd(S2CNEt2) shows the arrangement of the donor atoms is a distorted trigonal bipyramid, an unusual geometry for a molecule containing a tridentate [HB(3-Bu(1)pz)(3)](-) ligand. Mixing CdCl2 with 2 equiv. of MeLi yields the Me2Cd intermediate that reacts with Tl[HB(3-Phpz)(3)] to yield [HB(3-Phpz)(3)]CdCH3 (3). Compound 3 reacts with thiotoluene to yield [HB(3-Phpz)(3)]CdS(p-C6H4CH3) (4) and mercaptopyridine to yield [HB(3-Phpz)(3)]Cd(SNC6H4) (5). The neutral 2,6-bis(2,6-dimethylphenylimino)pyridine ligand (pydim) reacts with CdCl2 in equimolar amounts to yield the adduct (pydim)CdCl2 (6). The cadmium(II) is in a five-coordinate arrangement that is best described as a distorted trigonal bipyramid. The three nitrogen atoms of the planar pyridine ligand occupy an equatorial and both axial sites, but the intrinsic bite angle of the ligand forces a significant distortion in the axial bond angle. Compound 6 reacts with an equimolar amount of Na[Et2NCS2] to yield [(pydim)Cd(S2CNEt2)][Cl] (7). The reaction of equimolar amounts of pydimMe(2) and Cd(NO3)(2) yields (pydimMe(2))Cd(NO3)(2) (8). In the structure of this complex, one nitrate ligand is bidentate and the other monodentate. If the bidentate ligand is considered as occupying one site of a polyhedron, the structure of 8 can be considered as a trigonal bipyramid, very similar to that of 6. (C) 2002 Elsevier Science B.V. All rights reserved.
• Palladium complexes bearing aromatic Bis-aldimine N^N^N pincer ligands; activity as catalysts in the hydrogenation of carbon dioxide
  作者：Nonkululeko Miya、Edward Ocansey、Banothile C.E. Makhubela

  DOI：10.1016/j.poly.2023.116360

  日期：2023.5

  substituents in respect of electronic effects, choice of pincer ligand system backbone, and steric effects of the substituents and the role it has on the hydrogenation of CO2. These pincer complexes were investigated as catalysts in the hydrogenation of CO2 and were found to be efficient in the direct catalytic carbon dioxide hydrogenation to formate with the highest TON at 520.

  CO 2加氢可以作为使用CO 2作为C1碳源的途径，同时作为氢“储存”的手段。在此我们报告了新的吡啶-2,6-双(亚甲基)双(CH = NR)-氯化钯络合物的合成是(R = Ph, p -Br- C 6 H 4 , 2,6-二甲基-C 6 3 ）。所有配合物均通过1 H NMR、13充分表征C NMR、FT-IR、元素分析、质谱和单晶 X 射线衍射研究（如适用）。这项工作旨在调查和讨论取代基在电子效应、钳形配体系统主链的选择和取代基的空间效应方面的作用及其对 CO 2 加氢的作用。这些钳形配合物作为 CO 2氢化催化剂进行了研究，发现在直接催化二氧化碳氢化生成甲酸盐中非常有效，最高 TON 为 520。