1-(α-chloro-β-formylvinyl)-1',2',3',4',5'-pentamethylruthenocene | 188580-25-8

• 英文名称: 1-(α-chloro-β-formylvinyl)-1',2',3',4',5'-pentamethylruthenocene
• CAS: 188580-25-8
• 化学式: C₁₈H₂₁ClORu
• 分子量: 389.887
• InChiKey: QZVDUBKNODCGFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1-(α-chloro-β-formylvinyl)-1',2',3',4',5'-pentamethylruthenocene 在 NaOH 作用下， 以 1,4-二氧六环 、 水 为溶剂， 以91%的产率得到1-ethynyl-1′,2′,3′,4′,5′-pentamethylruthenocene
  参考文献：
  名称：

  Novel Structural Rearrangements Induced by Metal−Metal Interactions in Ruthenium(II) Ruthenocenyl- and (Pentamethylruthenocenyl)acetylide Complexes, RcC⋮CRuL₂(η⁵-C₅R₅) and Rc‘C⋮CRuL₂(η⁵-C₅R₅) [Rc = Ruthenocenyl, Rc‘ = Pentamethylruthenocenyl, L₂ = 2PPh₃ or Ph₂PCH₂CH₂PPh₂ (dppe), R = H or Me]

  摘要：

  The reaction of RcC=CH [Rc = (eta(5)-C5H5)Ru(eta(5)-C5H4)] with RuClL2(eta(5)-C5R5) [R = H or Me; L-2 = 2PPh(3) or Ph2PCH2CH2PPh2 (dppe)] in the presence of NH4PF6 and subsequent treatment with base gave Ru(II) ruthenocenylacetylide complexes RcC=CRuL2(eta(5)-C5R5) in good yields. In a similar manner, the pentamethylruthenocene analogues, Rc'C=CRuL2(eta(5)-C5R5) [Rc' = (eta(5)-C5Me5)Ru(eta(5)-C5H4)], were also prepared. Cyclic voltammograms of the complexes showed two reversible one-electron-oxidation processes, consisting of the processes [Ru(II)Ru'(II)] to [Ru(III)Ru'(II)] and then to [Ru(III)Ru(III)]. Chemical oxidation of the complexes induced novel structural rearrangement. The two-electron oxidation of complex RcC=CRu(PPh3)(2)(eta(5)-C5H5) afforded a kind of allenylidene complex, a cyclopentadienylidenethylidene complex, [(eta(5)-C5H5)Ru{mu-eta(6):eta(1)-C5H4C=C}Ru(PPh3)(2)(eta(5)-C5H5)](2+), in 90% yield. The one-electron oxidation of Rc'C=CRu(PPh3)(2)(eta(5)-C5H5) gave the vinylidene complex (Rc'CH=C)Ru(PPh3)(2)(eta(5)-C5H5) in 62% yield, while the two-electron oxidation led to the fulvene-vinylidene complex [(eta(6)-C5Me4CH2)Ru{mu-eta(5):eta(1)-C5H4CH=C}Ru(PPh3)(2)(eta(5)-C5R5)](2+) by an intramolecular hydrogen transfer in 59% yield.

  DOI：

  10.1021/om960732t
• 作为产物：
  描述：

  (η5-pentamethylcyclopentadienyl)(η5-acetylcyclopentadienyl)ruthenium(II) 、 N,N-二甲基甲酰胺 、 三氯氧磷 以 N,N-二甲基甲酰胺 为溶剂， 以92%的产率得到1-(α-chloro-β-formylvinyl)-1',2',3',4',5'-pentamethylruthenocene
  参考文献：
  名称：

  Novel Structural Rearrangements Induced by Metal−Metal Interactions in Ruthenium(II) Ruthenocenyl- and (Pentamethylruthenocenyl)acetylide Complexes, RcC⋮CRuL₂(η⁵-C₅R₅) and Rc‘C⋮CRuL₂(η⁵-C₅R₅) [Rc = Ruthenocenyl, Rc‘ = Pentamethylruthenocenyl, L₂ = 2PPh₃ or Ph₂PCH₂CH₂PPh₂ (dppe), R = H or Me]

  摘要：

  The reaction of RcC=CH [Rc = (eta(5)-C5H5)Ru(eta(5)-C5H4)] with RuClL2(eta(5)-C5R5) [R = H or Me; L-2 = 2PPh(3) or Ph2PCH2CH2PPh2 (dppe)] in the presence of NH4PF6 and subsequent treatment with base gave Ru(II) ruthenocenylacetylide complexes RcC=CRuL2(eta(5)-C5R5) in good yields. In a similar manner, the pentamethylruthenocene analogues, Rc'C=CRuL2(eta(5)-C5R5) [Rc' = (eta(5)-C5Me5)Ru(eta(5)-C5H4)], were also prepared. Cyclic voltammograms of the complexes showed two reversible one-electron-oxidation processes, consisting of the processes [Ru(II)Ru'(II)] to [Ru(III)Ru'(II)] and then to [Ru(III)Ru(III)]. Chemical oxidation of the complexes induced novel structural rearrangement. The two-electron oxidation of complex RcC=CRu(PPh3)(2)(eta(5)-C5H5) afforded a kind of allenylidene complex, a cyclopentadienylidenethylidene complex, [(eta(5)-C5H5)Ru{mu-eta(6):eta(1)-C5H4C=C}Ru(PPh3)(2)(eta(5)-C5H5)](2+), in 90% yield. The one-electron oxidation of Rc'C=CRu(PPh3)(2)(eta(5)-C5H5) gave the vinylidene complex (Rc'CH=C)Ru(PPh3)(2)(eta(5)-C5H5) in 62% yield, while the two-electron oxidation led to the fulvene-vinylidene complex [(eta(6)-C5Me4CH2)Ru{mu-eta(5):eta(1)-C5H4CH=C}Ru(PPh3)(2)(eta(5)-C5R5)](2+) by an intramolecular hydrogen transfer in 59% yield.

  DOI：

  10.1021/om960732t