Ditert-butyl-[[6-(ditert-butylphosphanylmethyl)-4-methylpyridin-2-yl]methyl]phosphane | 1449570-16-4

• 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: Ditert-butyl-[[6-(ditert-butylphosphanylmethyl)-4-methylpyridin-2-yl]methyl]phosphane
• 英文别名: ditert-butyl-[[6-(ditert-butylphosphanylmethyl)-4-methylpyridin-2-yl]methyl]phosphane
• CAS: 1449570-16-4
• 化学式: C₂₄H₄₅NP₂
• 分子量: 409.576
• InChiKey: OJXQIPOXXYFGBW-UHFFFAOYSA-N

物化性质

• 沸点：
  471.7±45.0 °C(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trichlorotris(tetrahydrofuran)molybdenum(III) 、 Ditert-butyl-[[6-(ditert-butylphosphanylmethyl)-4-methylpyridin-2-yl]methyl]phosphane 以 四氢呋喃 为溶剂， 以89%的产率得到[MoCl₃(4-methyl-2,6-bis(di-t-butylphosphino)methylpyridine)]
  参考文献：
  名称：

  Catalytic Formation of Ammonia from Molecular Dinitrogen by Use of Dinitrogen-Bridged Dimolybdenum–Dinitrogen Complexes Bearing PNP-Pincer Ligands: Remarkable Effect of Substituent at PNP-Pincer Ligand

  摘要：

  A series of dinitrogen-bridged dimolybdenum-dinitrogen complexes bearing 4-substituted PNP-pincer ligands are synthesized by the reduction of the corresponding molybdenum trichloride complexes under 1 atm of molecular dinitrogen. In accordance with a theoretical study, the catalytic activity is enhanced by the introduction of an electron-donating group to the pyridine ring of PNP-pincer ligand, and the complex bearing 4-methoxy-substituted PNP-pincer ligands is found to work as the most effective catalyst, where 52 equiv of ammonia are produced based on the catalyst (26 equiv of ammonia based on each molybdenum atom of the catalyst), together with molecular dihydrogen as a side-product. Time profiles for the catalytic reactions indicate that the rates of the formation of ammonia and molecular dihydrogen depend on the nature of the substituent on the PNP-pincer ligand of the complexes. The formation of ammonia and molecular dihydrogen is complementary in the reaction system.

  DOI：

  10.1021/ja5044243
• 作为产物：
  描述：

  2,4,6-三甲基吡啶 、 二叔丁基氯化膦 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 17.0h， 以37%的产率得到Ditert-butyl-[[6-(ditert-butylphosphanylmethyl)-4-methylpyridin-2-yl]methyl]phosphane
  参考文献：
  名称：

  Catalytic Formation of Ammonia from Molecular Dinitrogen by Use of Dinitrogen-Bridged Dimolybdenum–Dinitrogen Complexes Bearing PNP-Pincer Ligands: Remarkable Effect of Substituent at PNP-Pincer Ligand

  摘要：

  A series of dinitrogen-bridged dimolybdenum-dinitrogen complexes bearing 4-substituted PNP-pincer ligands are synthesized by the reduction of the corresponding molybdenum trichloride complexes under 1 atm of molecular dinitrogen. In accordance with a theoretical study, the catalytic activity is enhanced by the introduction of an electron-donating group to the pyridine ring of PNP-pincer ligand, and the complex bearing 4-methoxy-substituted PNP-pincer ligands is found to work as the most effective catalyst, where 52 equiv of ammonia are produced based on the catalyst (26 equiv of ammonia based on each molybdenum atom of the catalyst), together with molecular dihydrogen as a side-product. Time profiles for the catalytic reactions indicate that the rates of the formation of ammonia and molecular dihydrogen depend on the nature of the substituent on the PNP-pincer ligand of the complexes. The formation of ammonia and molecular dihydrogen is complementary in the reaction system.

  DOI：

  10.1021/ja5044243

文献信息

• Effect of substituents on molybdenum triiodide complexes bearing PNP-type pincer ligands toward catalytic nitrogen fixation
  作者：Takayuki Itabashi、Ikki Mori、Kazuya Arashiba、Aya Eizawa、Kazunari Nakajima、Yoshiaki Nishibayashi

  DOI：10.1039/c8dt04975k

  日期：——

  Molybdenum triiodide complexes bearing various substituted pyridine-based PNP-type pincer ligands are prepared and characterized by X-ray analysis. Their catalytic activity is investigated toward the reduction of nitrogen gas into ammonia under ambient reaction conditions.

  制备带有各种取代的吡啶基PNP型钳形配体的三碘化钼配合物，并通过X射线分析对其进行表征。研究了它们在环境反应条件下将氮气还原为氨的催化活性。
• Preparation and Reactivity of Rhenium–Nitride Complexes Bearing PNP-Type Pincer Ligands toward Nitrogen Fixation
  作者：Fanqiang Meng、Shogo Kuriyama、Akihito Egi、Hiromasa Tanaka、Kazunari Yoshizawa、Yoshiaki Nishibayashi

  DOI：10.1021/acs.organomet.2c00312

  日期：——

  rhenium(V)–nitride complexes bearing substituted pyridine-based PNP-type pincer ligands are synthesized. The substituent in the PNP-type pincer ligand does not significantly improve the catalytic activity for ammonia formation, while the introduction of a methoxy group increases the catalytic activity for the silylamine formation. Stoichiometric studies reveal that a rhenium(V)–nitride complex bearing a nonsubstituted

  合成了一系列带有取代吡啶基 PNP 型钳形配体的单核铼 (V)- 氮化物络合物。PNP型钳形配体中的取代基并没有显着提高氨形成的催化活性，而甲氧基的引入提高了甲硅烷基胺形成的催化活性。化学计量研究表明，带有未取代的 PNP 型钳形配体的铼 (V)- 氮化物络合物在还原条件下转化为脱芳构化的铼 (V)- 氮化物二聚体，而脱芳构化的铼 (V)- 氮化物二聚体表现出催化活性固氮反应。然而，带有甲基取代的 PNP 型钳形配体的铼 (V)- 氮化物络合物通过还原表现出不同的反应性，
• Catalytic Formation of Ammonia from Molecular Dinitrogen by Use of Dinitrogen-Bridged Dimolybdenum–Dinitrogen Complexes Bearing PNP-Pincer Ligands: Remarkable Effect of Substituent at PNP-Pincer Ligand
  作者：Shogo Kuriyama、Kazuya Arashiba、Kazunari Nakajima、Hiromasa Tanaka、Nobuaki Kamaru、Kazunari Yoshizawa、Yoshiaki Nishibayashi

  DOI：10.1021/ja5044243

  日期：2014.7.9

  A series of dinitrogen-bridged dimolybdenum-dinitrogen complexes bearing 4-substituted PNP-pincer ligands are synthesized by the reduction of the corresponding molybdenum trichloride complexes under 1 atm of molecular dinitrogen. In accordance with a theoretical study, the catalytic activity is enhanced by the introduction of an electron-donating group to the pyridine ring of PNP-pincer ligand, and the complex bearing 4-methoxy-substituted PNP-pincer ligands is found to work as the most effective catalyst, where 52 equiv of ammonia are produced based on the catalyst (26 equiv of ammonia based on each molybdenum atom of the catalyst), together with molecular dihydrogen as a side-product. Time profiles for the catalytic reactions indicate that the rates of the formation of ammonia and molecular dihydrogen depend on the nature of the substituent on the PNP-pincer ligand of the complexes. The formation of ammonia and molecular dihydrogen is complementary in the reaction system.