2,6-bis{[N-butyl]imidazole-1-ylidene-2-thione}pyridine | 1337540-02-9

• 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{[N-butyl]imidazole-1-ylidene-2-thione}pyridine
• 英文别名: 2,6-bis(3-n-butylimidazol-2-thione-1-yl)pyridine；1-Butyl-3-[6-(3-butyl-2-sulfanylideneimidazol-1-yl)pyridin-2-yl]imidazole-2-thione；1-butyl-3-[6-(3-butyl-2-sulfanylideneimidazol-1-yl)pyridin-2-yl]imidazole-2-thione
• CAS: 1337540-02-9
• 化学式: C₁₉H₂₅N₅S₂
• 分子量: 387.573
• InChiKey: QYAYWPGPMVZLTH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  90
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,6-bis{[N-butyl]imidazole-1-ylidene-2-thione}pyridine 、 copper dichloride 以 二氯甲烷 为溶剂， 反应 20.0h， 以95%的产率得到dichloro-[(η³-S,S,N)(2,6-bis){[N-butyl]imidazole-1-ylidene-2-thione}pyridine copper(II)]
  参考文献：
  名称：

  基于三齿SNS钳配体前体的五配位铜（II）配合物的合成与表征

  摘要：

  将基于双咪唑基前体的一系列三齿钳形配体（每个具有两个硫和一个氮供体官能团（SNS））用CuCl 2金属化，得到新的三齿SNS钳形铜（II）络合物[（SNS）CuCl 2 ]。这些紫色配合物在铜中心显示出五坐标的伪正方形金字塔几何形状。[（SNS）CuCl 2 ]配合物的特征在于单晶X射线衍射，电喷雾质谱，EPR光谱，衰减全反射红外光谱，UV-Vis光谱，循环伏安法和元素分析。EPR谱图与典型的各向异性Cu（II）信号一致，在较低的视场区域有四个超精细分裂（g ||）。各种电子跃迁在配合物的UV-Vis光谱中都很明显，并且源自d到d跃迁或各种电荷转移跃迁。我们进行了计算研究，以了解三齿SNS配体前体内部的结构约束对所得结合铜配合物的氧化态的影响。我们已经确定，当ad 9铜（II）金属中心不包含内部CH 2基团时，其结合我们的三齿SNS配体组的位置比ad 10铜（I）中心更好。如果没有该亚甲基

  DOI：

  10.1016/j.poly.2014.03.020
• 作为产物：
  描述：

  2,6-bis(3-butylimidazol-1-yl-3-ium)pyridine dibromide 在 sodium acetate 、 sulfur 作用下， 以 乙腈 为溶剂， 反应 168.5h， 以70%的产率得到2,6-bis{[N-butyl]imidazole-1-ylidene-2-thione}pyridine
  参考文献：
  名称：

  Syntheses, characterization, density functional theory calculations, and activity of tridentate SNS zinc pincer complexes

  摘要：

  A series of tridentate SNS ligand precursors were metallated with ZnCl2 to give new tridentate SNS pincer zinc complexes. The zinc complexes serve as models for the zinc active site in liver alcohol dehydrogenase (LADH) and were characterized with single crystal X-ray diffraction, H-1, C-13, and HSQC NMR spectroscopies and electrospray mass spectrometry. The bond lengths and bond angles of the zinc complexes correlate well to those in horse LADH. The zinc complexes feature SNS donor atoms and pseudotetrahedral geometry about the zinc center, as is seen for liver alcohol dehydrogenase. The SNS ligand precursors were characterized with H-1, C-13, and HSQC NMR spectroscopies and cyclic voltammetry, and were found to be redox active. Gaussian calculations were performed and agree quite well with the experimentally observed oxidation potential for the pincer ligand. The zinc complexes were screened for the reduction of electron poor aldehydes in the presence of a hydrogen donor, 1-benzyl-1,4-dihydronicotinamide (BNAH). The zinc complexes enhance the reduction of electron poor aldehydes. Density functional theory calculations were performed to better understand why the geometry about the zinc center is pseudo-tetrahedral rather than pseudo-square planar, which is seen for most pincer complexes. For the SNS tridentate pincer complexes, the data indicate that the pseudo-tetrahedral geometry was 43.8 kcal/mol more stable than the pseudo-square planar geometry. Density functional theory calculations were also performed on zinc complexes with monodentate ligands and the data indicate that the pseudo-tetrahedral geometry was 30.6 kcal/mol more stable than pseudo-square planar geometry. Overall, the relative stabilities of the pseudo-tetrahedral and pseudo-square planar systems are the same for this coordination environment whether the ligand set is a single tridentate SNS system or is broken into three separate units. The preference of a d(10) Zn center to attain a tetrahedral local environment trumps any stabilization gained by removal of constraints within the ligand set. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.07.021

文献信息

• Syntheses, characterization, density functional theory calculations, and activity of tridentate SNS zinc pincer complexes
  作者：John R. Miecznikowski、Wayne Lo、Matthew A. Lynn、Brianne E. O’Loughlin、Amanda P. DiMarzio、Anthony M. Martinez、Lorraine Lampe、Kathleen M. Foley、Lauren C. Keilich、George P. Lisi、Daniel J. Kwiecien、Cristina M. Pires、William J. Kelly、Nathan F. Kloczko、Kaitlyn N. Morio

  DOI：10.1016/j.ica.2011.07.021

  日期：2011.10

  A series of tridentate SNS ligand precursors were metallated with ZnCl2 to give new tridentate SNS pincer zinc complexes. The zinc complexes serve as models for the zinc active site in liver alcohol dehydrogenase (LADH) and were characterized with single crystal X-ray diffraction, H-1, C-13, and HSQC NMR spectroscopies and electrospray mass spectrometry. The bond lengths and bond angles of the zinc complexes correlate well to those in horse LADH. The zinc complexes feature SNS donor atoms and pseudotetrahedral geometry about the zinc center, as is seen for liver alcohol dehydrogenase. The SNS ligand precursors were characterized with H-1, C-13, and HSQC NMR spectroscopies and cyclic voltammetry, and were found to be redox active. Gaussian calculations were performed and agree quite well with the experimentally observed oxidation potential for the pincer ligand. The zinc complexes were screened for the reduction of electron poor aldehydes in the presence of a hydrogen donor, 1-benzyl-1,4-dihydronicotinamide (BNAH). The zinc complexes enhance the reduction of electron poor aldehydes. Density functional theory calculations were performed to better understand why the geometry about the zinc center is pseudo-tetrahedral rather than pseudo-square planar, which is seen for most pincer complexes. For the SNS tridentate pincer complexes, the data indicate that the pseudo-tetrahedral geometry was 43.8 kcal/mol more stable than the pseudo-square planar geometry. Density functional theory calculations were also performed on zinc complexes with monodentate ligands and the data indicate that the pseudo-tetrahedral geometry was 30.6 kcal/mol more stable than pseudo-square planar geometry. Overall, the relative stabilities of the pseudo-tetrahedral and pseudo-square planar systems are the same for this coordination environment whether the ligand set is a single tridentate SNS system or is broken into three separate units. The preference of a d(10) Zn center to attain a tetrahedral local environment trumps any stabilization gained by removal of constraints within the ligand set. (C) 2011 Elsevier B.V. All rights reserved.
• Syntheses and characterization of five-coordinate copper(II) complexes based on tridentate SNS pincer ligand precursors
  作者：John R. Miecznikowski、Matthew A. Lynn、Jerry P. Jasinski、Wayne Lo、Daniel W. Bak、Mekhala Pati、Elizabeth E. Butrick、Anne Elise R. Drozdoski、Kerry A. Archer、Christine E. Villa、Elise G. Lemons、Erin Powers、Margaret Siu、Camile D. Gomes、Nicholas A. Bernier、Kaitlyn N. Morio

  DOI：10.1016/j.poly.2014.03.020

  日期：2014.9

  spectrometry, EPR spectroscopy, attenuated total reflectance infrared spectroscopy, UV–Vis spectroscopy, cyclic voltammetry, and elemental analysis. The EPR spectra are consistent with typical anisotropic Cu(II) signals with four hyperfine splittings in the lower-field region (g||). Various electronic transitions are apparent in the UV–Vis spectra of the complexes and originate from d-to-d transitions or

  将基于双咪唑基前体的一系列三齿钳形配体（每个具有两个硫和一个氮供体官能团（SNS））用CuCl 2金属化，得到新的三齿SNS钳形铜（II）络合物[（SNS）CuCl 2 ]。这些紫色配合物在铜中心显示出五坐标的伪正方形金字塔几何形状。[（SNS）CuCl 2 ]配合物的特征在于单晶X射线衍射，电喷雾质谱，EPR光谱，衰减全反射红外光谱，UV-Vis光谱，循环伏安法和元素分析。EPR谱图与典型的各向异性Cu（II）信号一致，在较低的视场区域有四个超精细分裂（g ||）。各种电子跃迁在配合物的UV-Vis光谱中都很明显，并且源自d到d跃迁或各种电荷转移跃迁。我们进行了计算研究，以了解三齿SNS配体前体内部的结构约束对所得结合铜配合物的氧化态的影响。我们已经确定，当ad 9铜（II）金属中心不包含内部CH 2基团时，其结合我们的三齿SNS配体组的位置比ad 10铜（I）中心更好。如果没有该亚甲基