6-(N-di-tert-butylphosphino)-2-(2'-methyl-2'H-benzoimidazole)aminepyridine | 1415800-77-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并咪唑类
• 英文名称: 6-(N-di-tert-butylphosphino)-2-(2'-methyl-2'H-benzoimidazole)aminepyridine
• 英文别名: N-ditert-butylphosphanyl-6-(1-methylbenzimidazol-2-yl)pyridin-2-amine
• CAS: 1415800-77-9
• 化学式: C₂₁H₂₉N₄P
• 分子量: 368.462
• InChiKey: GZYKDDDVZKHIHY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  42.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-(N-di-tert-butylphosphino)-2-(2'-methyl-2'H-benzoimidazole)aminepyridine 、 cobalt(II) chloride 以 四氢呋喃 为溶剂， 生成 N-ditert-butylphosphanyl-6-(1-methylbenzimidazol-2-yl)pyridin-2-amine;dichlorocobalt
  参考文献：
  名称：

  Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization

  摘要：

  Incomplete oxidation of (N-di-tert-butylphosphino)-6-(2-methyl-2'H-benzoimidazole)-2-aminepyridine dichlorocobalt ((PNCoCl2)-Co-3) in DMF results in a unique co-crystal I formed with three parts including DMF, unit A and unit B complex with Co1 and Co2, respectively (PN3 ligand in unit A: (N-di-tertbutylphosphino)-6-(2'-methyl-2'H-benzoimidazole)-2-aminepyridine, and O=PN3 ligand in unit B: (N-di-tert-butylphosphinoxide)-6-(2'-methyl-2'H-benzoimidazole)-2-aminepyridine), with 1:1:1 molar ratio. Co1 and Co2 complexes both display a five-coordinated distorted-square-pyramidal geometry around the metal center. The Co1 center is coordinated with PN3 ligand via two N atoms from pyridine, benzoimidazole moiety as well as one P atom, and the Co2 center is coordinated with the oxidized ligand O=PN3 via two N atoms from pyridine, benzoimidazole moiety as well as one O atom from DMF molecule, while the oxidized phosphine moiety (O=P) being excluded from the coordination sphere. Activated with AlEt2Cl, the co-crystallized complexes I are able to actively convert butadiene to polybutadiene, affording cis-1,4 polybutadiene with cis-1,4 unit up to 95.5-97.8% and number average molecular weight of cal. 10(5) g/mol. The high cis-1,4 selectivity and monomodal GPC curve of resultant polymer imply that the identical active species generated from two distinctive cobalt centers. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2015.07.033
• 作为产物：
  描述：

  2-(6-bromopyridin-2-yl)-1H-benzo[d]imidazole 在 copper(I) oxide 、 正丁基锂 、 氨 、 三乙胺 、 potassium hydroxide 作用下， 以 正己烷 、 乙二醇 、 甲苯 为溶剂， -78.0~110.0 ℃ 、1.01 MPa 条件下， 反应 24.0h， 生成 6-(N-di-tert-butylphosphino)-2-(2'-methyl-2'H-benzoimidazole)aminepyridine
  参考文献：
  名称：

  Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization

  摘要：

  Incomplete oxidation of (N-di-tert-butylphosphino)-6-(2-methyl-2'H-benzoimidazole)-2-aminepyridine dichlorocobalt ((PNCoCl2)-Co-3) in DMF results in a unique co-crystal I formed with three parts including DMF, unit A and unit B complex with Co1 and Co2, respectively (PN3 ligand in unit A: (N-di-tertbutylphosphino)-6-(2'-methyl-2'H-benzoimidazole)-2-aminepyridine, and O=PN3 ligand in unit B: (N-di-tert-butylphosphinoxide)-6-(2'-methyl-2'H-benzoimidazole)-2-aminepyridine), with 1:1:1 molar ratio. Co1 and Co2 complexes both display a five-coordinated distorted-square-pyramidal geometry around the metal center. The Co1 center is coordinated with PN3 ligand via two N atoms from pyridine, benzoimidazole moiety as well as one P atom, and the Co2 center is coordinated with the oxidized ligand O=PN3 via two N atoms from pyridine, benzoimidazole moiety as well as one O atom from DMF molecule, while the oxidized phosphine moiety (O=P) being excluded from the coordination sphere. Activated with AlEt2Cl, the co-crystallized complexes I are able to actively convert butadiene to polybutadiene, affording cis-1,4 polybutadiene with cis-1,4 unit up to 95.5-97.8% and number average molecular weight of cal. 10(5) g/mol. The high cis-1,4 selectivity and monomodal GPC curve of resultant polymer imply that the identical active species generated from two distinctive cobalt centers. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2015.07.033

文献信息

• PHOSPHO-AMINO PINCER-TYPE LIGANDS AND CATALYTIC METAL COMPLEXES THEREOF
  申请人：Huang Kuo-Wei

  公开号：US20120323007A1

  公开（公告）日：2012-12-20

  The present invention provides phospho-amino pincer-type ligands, metal complexes thereof, and catalytic methods comprising such metal complexes.

  本发明提供了磷酸氨基夹持型配体、其金属配合物以及包括这种金属配合物的催化方法。
• A robust NNP‐type ruthenium (II) complex for alcohols dehydrogenation to esters and pyrroles
  作者：Huining Chai、Guangyao Zhang、Weiqiang Tan、Jiping Ma

  DOI：10.1002/aoc.5367

  日期：2020.2

  (II) complex bearing pyridyl‐based benzimidazole‐phosphine tridentate NNP ligand was synthesized and structurally characterized by NMR, IR. The complex can efficiently and selectively catalyze the acceptorless dehydrogenation of primary alcohols to esters under relatively mild conditions and the synthesis of pyrroles by means of the reactions of secondary alcohols and β‐amino alcohols through acceptorless

  合成了带有吡啶基苯并咪唑膦三齿NNP配体的Ru（II）配合物，并通过NMR，IR对其结构进行了表征。该络合物可以在相对温和的条件下有效地，选择性地催化伯醇的无受体脱氢成酯，并通过仲醇和β-氨基醇通过无受体的脱氧缩合反应来合成吡咯。
• Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization
  作者：Wen Liu、Weijing Pan、Peng Wang、Wei Li、Jingshan Mu、Gengsheng Weng、Xiaoyu Jia、Dirong Gong、Kuo-Wei Huang

  DOI：10.1016/j.ica.2015.07.033

  日期：2015.9

  Incomplete oxidation of (N-di-tert-butylphosphino)-6-(2-methyl-2'H-benzoimidazole)-2-aminepyridine dichlorocobalt ((PNCoCl2)-Co-3) in DMF results in a unique co-crystal I formed with three parts including DMF, unit A and unit B complex with Co1 and Co2, respectively (PN3 ligand in unit A: (N-di-tertbutylphosphino)-6-(2'-methyl-2'H-benzoimidazole)-2-aminepyridine, and O=PN3 ligand in unit B: (N-di-tert-butylphosphinoxide)-6-(2'-methyl-2'H-benzoimidazole)-2-aminepyridine), with 1:1:1 molar ratio. Co1 and Co2 complexes both display a five-coordinated distorted-square-pyramidal geometry around the metal center. The Co1 center is coordinated with PN3 ligand via two N atoms from pyridine, benzoimidazole moiety as well as one P atom, and the Co2 center is coordinated with the oxidized ligand O=PN3 via two N atoms from pyridine, benzoimidazole moiety as well as one O atom from DMF molecule, while the oxidized phosphine moiety (O=P) being excluded from the coordination sphere. Activated with AlEt2Cl, the co-crystallized complexes I are able to actively convert butadiene to polybutadiene, affording cis-1,4 polybutadiene with cis-1,4 unit up to 95.5-97.8% and number average molecular weight of cal. 10(5) g/mol. The high cis-1,4 selectivity and monomodal GPC curve of resultant polymer imply that the identical active species generated from two distinctive cobalt centers. (C) 2015 Elsevier B.V. All rights reserved.