benzonitrile;(3,5-dimethylphenyl)-[2-[2-(3,5-dimethylphenyl)azanidylphenyl]sulfanylphenyl]azanide;ruthenium(2+);trimethylphosphane | 472969-08-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: benzonitrile;(3,5-dimethylphenyl)-[2-[2-(3,5-dimethylphenyl)azanidylphenyl]sulfanylphenyl]azanide;ruthenium(2+);trimethylphosphane
• CAS: 472969-08-7
• 化学式: C₄₁H₄₉N₃P₂RuS
• 分子量: 778.944
• InChiKey: HCSVAVAXBHZYAQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.02
• 重原子数：
  48
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  51.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  、 苯甲腈 以 甲苯 为溶剂， 以49%的产率得到benzonitrile;(3,5-dimethylphenyl)-[2-[2-(3,5-dimethylphenyl)azanidylphenyl]sulfanylphenyl]azanide;ruthenium(2+);trimethylphosphane
  参考文献：
  名称：

  Ruthenium Complexes Containing Bis(diarylamido)/Thioether Ligands:  Synthesis and Their Catalysis for the Hydrogenation of Benzonitrile

  摘要：

  Treatment of the thioethers (RNH-o-C6H4)(2)S (H-2[R2NSN]; R = Xy, Xyf; Xy = 3,5-Me2C6H3, Xyf = 3,5-(CF3)(2)C6H3) with 2 equiv of n-BuLi followed by addition of 0.5 equiv of [(eta(6)-C6H6)RuCl2](2) in THF gave the bis(diarylamido)/thioether complexes [(eta(6)-C6H6)Ru[R2NSN]] (R = Xy (1a), R = Xyf (1b)) in moderate yields. In the presence of la (1 mol %) and PCy3 (2 mol %; Cy = cyclohexyl), benzonitrile was catalytically hydrogenated to give benzylamine (72%) and benzylidenebenzylamine (27%) at 80 degreesC and 30 atm, while the hydrogenation with 1b as a catalyst precursor resulted in the formation of benzylamine (37%) and benzylidenebenzylamine (51%) under the same reaction conditions. The yield of benzylamine was improved up to 92% by using a catalyst mixture of la (1 mol %)/PCy3 (2 mol %)/t-BuONa (10 mol %). On the other hand, the reaction of la with excess PMe3 afforded the tris(trimethylphosphine) derivative [(PMe3)(3)Ru[Xy(2)NSN]] (2). Treatment of 2 with excess PhCN, MeCN, or N2H4.H2O resulted in the replacement of a PMe3 ligand by these substrates to give [(PMe3)(2)LRu[Xy(2)NSN]] (3, L = PhCN; 4, L = MeCN; 5, L = N2H4), while the reaction of 2 with benzoylhydrazine gave the kappa(2)-benzoylhydrazido complex [(PMe3)(2)Ru(kappa(2)-(O,N)-PhC(O)=NNH2)(H[Xy(2)NSN])] (6). Structures of la, 1b, 2, 5, and 6 have been determined by X-ray crystallography.

  DOI：

  10.1021/om020340o