2,6-bis[(1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine | 946828-70-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2,6-bis[(1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine
• 英文别名: 1,3-ditert-butyl-N-[[6-[[(1,3-ditert-butylimidazol-2-ylidene)amino]methyl]pyridin-2-yl]methyl]imidazol-2-imine
• CAS: 946828-70-2
• 化学式: C₂₉H₄₇N₇
• 分子量: 493.739
• InChiKey: FPVDSOQKFCSPHE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,6-bis[(1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine 在 NaCl 、 NaClO₄ 作用下， 以 水 为溶剂， 生成 (2,6-bis[(1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine)(dimethylsulfoxide)platinum(II)
  参考文献：
  名称：

  Ligand substitution reactions of some sterically hindered Pt(II) complexes. The crystal structures of [TLBuH2](ClO4)2·0.5H2O

  摘要：

  Substitution reactions of the complexes [(TLtBu)PtCl](+) and [Pt(tpdm)Cl](+), where TLtBu = 2,6-bis[(1,3-ditert-butylimidazolin-2-imino)methyl]pyridine and tpdm = terpyridinedimethane, with nucleophiles: thiourea, I-, Br-, NO2-, pyridine and dimethyl-sulfoxide (DMSO) were studied in 0.1 M NaClO4 aqueous solution in the presence of 10 mM NaCl. The reactions were carried out at three different temperatures (288, 298 and 308 K) using variable-temperature UV-VIS spectrophotometer. The substitutions were followed under the pseudo-first-order conditions with a large excess of nucleophiles. The slightly higher reactivity of complex with tpdm ligand can be attributed to the influence of the bulkiness of tertbutyl-groups from [(TLtBu)PtCl](+) complex. The order of reactivity of studied ligands is: thiourea > I- > Br- > NO2- > pyridine > DMSO. The negative values reported for entropy of activation confirmed the associative substitution mode. These results are discussed in order to find the connection between structure and reactivity of the complexes with tridentate sterically hindered ligands. The crystal structure of [(TLH2)-H-tBU](ClO4)(2)center dot 0.5H(2)O was determined by X-ray diffraction. (c) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.04.024
• 作为产物：
  描述：

  在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以95%的产率得到2,6-bis[(1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine
  参考文献：
  名称：

  含双（咪唑啉-2-亚胺）钳型配体的铜（I）配合物的合成和反应性。

  摘要：

  从2,6-双（羟甲基）吡啶高收率制备了新的钳位配体2,6-双[（1,3-二叔丁基咪唑啉-2-亚氨基）甲基]吡啶（TL（tBu）） （1）和1,3-二叔丁基咪唑啉-2-亚胺（3）。TL（tBu）与[Cu（MeCN）4] PF6的反应提供了高反应性的铜（I）络合物[（TL（tBu））Cu] PF6，[5] PF6，形成了稳定的异氰酸铜（I）络合物[6a] PF6（nu（CN）= 2179 cm（-1））和[6b] PF6（nu（CN）= 2140 cm（-1）），分别加入叔丁基或2,6-二甲基苯基异氰化物。对于阳离子6a和6b，DFT计算揭示了[[TL（tBu）-kappaN（1）：kappaN（2））Cu（CNR）类型的基态电子结构，其三坐标几何形状围绕铜原子。[5] PF6暴露于空气中很容易导致大气中的CO2截留，从而形成方形复合物[（TL（tBu））Cu（HCO3-kappaO）] PF6，[7]

  DOI：

  10.1039/b703183a

文献信息

• Equilibrium studies of the reactions of palladium(ii) bis(imidazolin-2-imine) complexes with biologically relevant nucleophiles. The crystal structures of [(TLtBu)PdCl]ClO4 and [(BLiPr)PdCl2]
  作者：Jovana Bogojeski、Ratomir Jelić、Dejan Petrović、Eberhardt Herdtweck、Peter G. Jones、Matthias Tamm、Živadin D. Bugarčić

  DOI：10.1039/c1dt10289c

  日期：——

  followed by L-His and L-Met for both complexes, [(BLiPr)Pd(H2O)2]2+ and [(TLtBu)Pd(H2O)]2+. The crystal structures of [(TLtBu)PdCl]ClO4 and [(BLiPr)PdCl2] were determined by X-ray diffraction. The coordination geometries around the palladium atoms are distorted square-planar, with the Pd–N1 distance to the central nitrogen atom of the TLtBu ligand, 1.944(2) Å, being shorter than those to the other two nitrogen

  络合物[（TL t Bu）PdCl] +的动力学和取代反应的机理，其中TL t Bu为2,6-双[（1,3-二叔丁基咪唑啉-2-亚氨基）甲基]吡啶，带有亲核试剂（鸟苷-5'-单磷酸酯 （5′-GMP）， L-蛋氨酸 （大号-Met） 和 L-组氨酸 （大号-His））在298 K下在0.1 M NaClO 4水溶液和10 mM NaCl中使用可变温度停止流技术进行了研究。反应顺序为：大号-Met > 5′-GMP> 大号-His。[（BL i Pr）Pd（H 2 O）2 ] 2+的形成平衡，其中BL i Pr是1,2-双（1,3二异丙基-4,5-二甲基咪唑啉-2-亚氨基）乙烷和[ （TL t Bu）Pd（H 2 O）] 2+和一些生物学相关的配体（大号-Met，5'-GMP和 大号-His）也进行了研究。报告了新形成的配合物的化学计量和稳定性常数，并评估了各种配合物种类的浓度分布与pH的关系。日志的值进行比较β
• Transition Metal Complexes Containing<i>C</i>₂-Symmetric Bis(imidazolin-2-imine) Ligands Derived from a 1-Alkyl-3-arylimidazolin-2-ylidene
  作者：Thomas Glöge、Frouke Aal、Sabina-Alexandra Filimon、Peter G. Jones、Janna Michaelis de Vasconcellos、Sonja Herres-Pawlis、Matthias Tamm

  DOI：10.1002/zaac.201500569

  日期：2015.10

  ethylene-bridged diimine ligand N,N′-bis[1-(2, 6-diisopropylphenyl)-3, 4,5-trimethylimidazolin-2-ylidene]-1, 2-ethanediamine, (IPrMe)NCH2CH2N(IPrMe) (5) was prepared by reaction of 4 with 1, 2-ethyleneditosylate and subsequent deprotonation with KOtBu. The reaction of 5 with metal dichlorides furnished the tetrahedral complexes [(5)MCl2] [M = Fe (6), M = Ni (7), M = Zn (8)] and the square-planar complex [(5)PdCl2]

  新的 N-杂环卡宾 1-(2, 6-二异丙基苯基)-3, 4,5-三甲基咪唑啉-2-亚基 (IPrMe) (3) 由异硫氰酸甲酯和 2, 6-二异丙基苯胺分三步制备，得到 N -甲基-N'-2, 6-二异丙基硫脲 (1)。1 与 3-羟基丁酮反应得到咪唑啉-2-硫酮 (IPrMe)S (2)，然后用元素钾将其还原为卡宾 IPrMe (3)。在沸腾的甲苯中用三甲基甲硅烷基叠氮化物 (Me3SiN3) 处理 3，然后在甲醇中脱甲硅烷基化，得到咪唑啉-2-亚胺 (IPrMe)NH (4)。乙烯桥连二亚胺配体 N,N'-双[1-(2, 6-diisopropylphenyl)-3, 4,5-trimethylimidazolin-2-ylidene]-1, 2-乙二胺, (IPrMe)NCH2CH2N(IPrMe) ( 5) 是通过 4 与 1, 2-亚乙基二甲苯磺酸酯反应和随后与 KOtBu 去质子化制备的。5
• 3d Metal Complexes Supported by a Bis(imidazolin‐2‐imino)pyridine Pincer Ligand – Synthesis, Structural Characterisation, and Magnetic Properties
  作者：Sabina‐Alexandra Filimon、Dejan Petrovic、Jeroen Volbeda、Thomas Bannenberg、Peter G. Jones、Carl‐Georg Freiherr von Richthofen、Thorsten Glaser、Matthias Tamm

  DOI：10.1002/ejic.201402804

  日期：2014.12

  coordination chemistry of the tridentate pincer ligand TLtBu, which contains two electron-rich imidazolin-2-imine moieties, has been explored. The reaction of TLtBu with metal dihalides gave complexes of the general formula [(TLtBu)-MX2] (M = Mn, Fe, Co, Ni; X = Cl, Br). These complexes were characterized by X-ray diffraction analysis, which showed them to have different geometries in the solid state. Although

  已经探索了包含两个富电子咪唑啉-2-亚胺部分的三齿钳状配体 TLtBu 的配位化学。TLtBu 与金属二卤化物反应生成通式为 [(TLtBu)-MX2] 的配合物（M = Mn、Fe、Co、Ni；X = Cl、Br）。这些配合物通过 X 射线衍射分析表征，表明它们在固态下具有不同的几何形状。尽管 [(TLtBu) MnCl2] (1) 最好被描述为扭曲的方形锥体，但复合物 [(TLtBu) FeCl2] (2) 和 [(TLtBu) CoCl2] (3) 显示出扭曲的四面体几何形状，其中 TLtBu 配体结合在kappa(2) 方式及其未与金属原子配位的咪唑啉-2-亚胺片段之一。[(TLtBu) NiBr]Br (4) 结晶时带有轻微扭曲的方形平面阳离子。三氟甲磺酸 (OTf) 盐 [M(OTf)(2) 中心点 nMeCN]（M = Mn，n = 1；M = Fe，Co，n = 2；OTf
• Syntheses and structures of lanthanide complexes containing a bis(imidazolin-2-imino)pyridine pincer ligand
  作者：Tarun K. Panda、Dejan Petrovic、Thomas Bannenberg、Cristian G. Hrib、Peter G. Jones、Matthias Tamm

  DOI：10.1016/j.ica.2007.11.027

  日期：2008.6

  The Lewis acid-base reaction of 2,6-bis[1,3-di-tert-butylimidazolin-2-imino) methyl] pyridine (TL(tBu)) and LnCl(3) in THF leads to the corresponding neutral lanthanide complexes of type [(TL(tBu)) LnCl(3)], Ln = Y (1a), Er (1b), Lu (1c). The yttrium and lutetium complexes have been characterized by X-ray diffraction analysis. The solid state structures reveal that the bulky TL(tBu) ligand causes steric crowding around the lanthanide atoms by coordinating to the metal center in a tridentate fashion. In addition, remote C-H center dot center dot center dot Ln interactions (H center dot center dot center dot Ln ca. 2.7 angstrom) involving one of the (t)Bu methyl groups are observed in both cases. A DFT (density functional theory) calculation on 1a was able to reproduce this interaction, which was additionally characterized by means of an H center dot center dot center dot Y compliance constant and by employing the AIM (atoms in molecules) theory. (C) 2007 Elsevier B. V. All rights reserved.