Ditert-butyl-[[6-(ditert-butylphosphinothioylmethyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl]methyl]-sulfanylidene-lambda5-phosphane | 1616367-31-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: Ditert-butyl-[[6-(ditert-butylphosphinothioylmethyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl]methyl]-sulfanylidene-lambda5-phosphane
• 英文别名: ditert-butyl-[[6-(ditert-butylphosphinothioylmethyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl]methyl]-sulfanylidene-λ5-phosphane
• CAS: 1616367-31-7
• 化学式: C₂₉H₅₄BNO₂P₂S₂
• 分子量: 585.644
• InChiKey: VOUWTNZJMMDQJV-UHFFFAOYSA-N

物化性质

• 沸点：
  631.8±65.0 °C(predicted)
• 密度：
  1.05±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.53
• 重原子数：
  37.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  31.35
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  Ditert-butyl-[[6-(ditert-butylphosphinothioylmethyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl]methyl]-sulfanylidene-lambda5-phosphane 在 四(三苯基膦)钯 、 potassium carbonate 、 三氟甲烷磺酸甲酯 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 67.0h， 生成 Ditert-butyl-[[6-(ditert-butylphosphanylmethyl)-4-phenylpyridin-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
• 作为产物：
  描述：

  2,6-二甲基吡啶 在 正丁基锂 、 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 四甲基乙二胺 、 4,4'-二叔丁基-2,2'-二吡啶 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 44.0h， 生成 Ditert-butyl-[[6-(ditert-butylphosphinothioylmethyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl]methyl]-sulfanylidene-lambda5-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

• Catalytic Activity of Molybdenum Complexes Bearing PNP‐Type Pincer Ligand toward Ammonia Formation
  作者：Taichi Mitsumoto、Yuya Ashida、Kazuya Arashiba、Shogo Kuriyama、Akihito Egi、Hiromasa Tanaka、Kazunari Yoshizawa、Yoshiaki Nishibayashi

  DOI：10.1002/anie.202306631

  日期：2023.10.23

  novel molybdenum complex bearing a 4-[3,5-bis(trifluoromethyl)phenyl]pyridine-based PNP-type pincer ligand, based on the bond dissociation free energies of the N−H bonds in molybdenum-imide complexes bearing various substituted PNP pincer ligands. The complex worked as an excellent catalyst toward ammonia formation, where up to 3580 equivalents of ammonia were formed based on the molybdenum atom of

  基于钼酰亚胺中 N−H 键的键解离自由能，我们新设计并制备了一种新型钼配合物，该配合物带有 4-[3,5-双（三氟甲基）苯基]吡啶基 PNP 型钳配体带有各种取代的 PNP 钳配体的复合物。该配合物是一种极好的氨形成催化剂，基于催化剂的钼原子可形成高达 3580 当量的氨。
• Design, synthesis and reactivity of dimolybdenum complex bearing quaterphenylene-bridged pyridine-based PNP-type pincer ligand
  作者：Aya Eizawa、Kazuya Arashiba、Hiromasa Tanaka、Asuka Konomi、Kazunari Yoshizawa、Yoshiaki Nishibayashi

  DOI：10.1039/d3dt02887a

  日期：——

  Dimolybdenum complexes bearing 3,3′′′-(1,1′:3′,1′′:3′′,1′′′-quaterphenylene)-bridged pyridine-based PNP-type pincer ligand are designed and prepared according to DFT calculations on the cleavage step of dinitrogen-bridged dimolybdenum complexes bearing polyphenylene-bridged pyridine-based PNP-type pincer ligands. The dimolybdenum complexes are found to work as effective catalysts toward ammonia formation

  根据以下方法设计并制备了带有3,3′′′-(1,1′:3′,1′′:3′′,1′′′-四联亚苯基)桥联吡啶基PNP型钳配体的二钼配合物带有聚亚苯基桥联吡啶基 PNP 型钳配体的二氮桥联二钼配合物裂解步骤的 DFT 计算。发现二钼络合物可作为在环境反应条件下以二碘化钐作为还原剂和水作为质子源从二氮形成氨的有效催化剂。