ruthenium(1+) monohydride;trimethylphosphane;hexafluorophosphate | 78789-92-1

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: ruthenium(1+) monohydride;trimethylphosphane;hexafluorophosphate
• CAS: 78789-92-1
• 化学式: C₁₅H₄₆P₅Ru*F₆P
• 分子量: 627.433
• InChiKey: QCXKKFRCMCYGSA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.9
• 重原子数：
  28
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  (η3-cyclooctenyl)tris(trimethylphosphine)ruthenium(II) hexafluorophosphate 、 三甲基膦 以 乙醇 、 丙酮 为溶剂， 生成 ruthenium(1+) monohydride;trimethylphosphane;hexafluorophosphate
  参考文献：
  名称：

  η 3 -Allyruthenium（II）配合物用作替代和二烯配位体的异构化中间体; 空间效应的主导作用

  摘要：

  的[Ru（形成η 3 -C 8 ħ 13）L- 3 ] PF 6如[期RuH（COD）L的转换中间体3 ] PF 6 [COD =环辛-1,5-二烯，L = PMe 3，P（OMe）2 Ph，PMe 2 Ph，P（OMe）Ph 2和P（OCH 2 CMe 3）3 ]变成[RuHL 4（solvent）] PF 6 [L = P（OMe）Ph 2和P（OCH 2 CMe 3）3 ]和[RuHL 5 ] PF 6 [L = PMe在图3中，已经显示出P（OMe） 2 Ph和PMe 2 Ph]和环辛基-1,3-二烯取决于L的大小。

  DOI：

  10.1039/c39820000214

文献信息

• Catalytic Behavior of Cationic Hydridoruthenium(II) Complex, [RuH(NH₃)(PMe₃)₄]⁺, in H₂-Hydrogenation and Transfer Hydrogenation of Imines
  作者：Yoshihito Kayaki、Hibiki Ikeda、Jun-ichirou Tsurumaki、Isao Shimizu、Akio Yamamoto

  DOI：10.1246/bcsj.81.1053

  日期：2008.9.15

  Catalytic hydrogenation under H2 and transfer hydrogenation of imines by secondary alcohols with hydridoruthenium complexes bearing PMe3 and PPh3 ligands have been examined. A cationic hydridoruthenium complex, cis-[RuH(NH3)(PMe3)4]PF6 (2), derived from cis-[RuH2(PMe3)4] (1) and NH4PF6, showed higher catalytic activity for H2-hydrogenation of N-benzylideneaniline than neutral complexes such as 1 and cis-[RuClH(PMe3)4] (6). The effectiveness of cationic hydridoruthenium species for the catalytic H2-hydrogenation of benzylideneaniline was also demonstrated by a marked increase in the yield of N-benzylaniline on treatment of 6 with AgPF6. The cationic complex 2 was applicable to catalytic transfer hydrogenation of imines with secondary alcohols even in the absence of a base. Isotope labeling experiments using deuterated alcohols revealed that the hydrogen atom bound to the α-carbon of the donor alcohol was transferred exclusively to the imine carbon and alcoholic OD was transferred to the imine nitrogen. A rapid exchange between the alcoholic proton and the hydrido ligand of 2 was also confirmed by NMR investigation using (CH3)2CHOD. On the basis of the experimental results the mechanisms of the H2-hydrogenation and transfer hydrogenation are discussed.

  通过带有PMe3和PPh3配体的氢化钌络合物，对H2催化氢化和二级醇转移氢化的亚胺进行了研究。从cis-[RuH2(PMe3)4] (1)和NH4PF6衍生出的阳离子氢化钌络合物cis-[RuH(NH3)(PMe3)4]PF6 (2)，比中性络合物1和cis-[RuClH(PMe3)4] (6)对N-苄亚胺的H2氢化表现出更高的催化活性。阳离子氢化钌物种对苄亚胺的催化H2氢化效果也可通过用AgPF6处理6得到N-苄胺产率显著增加来证明。阳离子络合物2即使在无碱条件下，也可适用于二级醇对亚胺的催化转移氢化。使用氘标记醇的同位素标记实验揭示，供体醇α-碳上的氢原子完全转移至亚胺碳，而醇的OD则转移至亚胺氮。通过使用(CH3)2CHOD的NMR研究还证实了2的氢配合物与醇质子之间的快速交换。根据实验结果，讨论了H2氢化和转移氢化的机理。