(η5-pentamethylcyclopentadienyl)(η5-acetylcyclopentadienyl)ruthenium(II) | 115560-13-9

• 英文名称: (η5-pentamethylcyclopentadienyl)(η5-acetylcyclopentadienyl)ruthenium(II)
• 英文别名: 1-acetyl-1',2',3',4',5'-pentamethylruthenocene；acetylpentamethylruthenocene
• CAS: 115560-13-9
• 化学式: C₁₇H₂₂ORu
• 分子量: 343.431
• InChiKey: VBQQMUGKGRYESS-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：

  (η5-pentamethylcyclopentadienyl)(η5-acetylcyclopentadienyl)ruthenium(II) 在 TiCl₄ 、 Zn 、 aq. K₂CO₃ 作用下， 以 四氢呋喃 、 水 为溶剂， 生成 cis-1,2-dimethyl-1,2-bis(1',2',3',4',5'-pentamethylruthenocenyl)ethylene 、 trans-1,2-dimethyl-1,2-bis(1',2',3',4',5'-pentamethylruthenocenyl)ethylene
  参考文献：
  名称：

  Synthesis, structure and redox chemistry of 1,2-bis(ruthenocenyl)ethylene derivatives: a novel structural rearrangement to a (μ-η6∶η6-pentafulvadiene)diruthenium complex upon two-electron oxidation

  摘要：

  2-双(钌烯基)乙烯、反式-1,2-双(1,2,3,4,5-五甲基钌烯基)乙烯和反式-1,2-双(2,3,4,5-四甲基钌烯基)乙烯的相应乙烯衍生物，收率极高。同样，从乙酰基二茂钌和 1-乙酰基-1,2,3,4,5,5-五甲基二茂钌中也能以良好的收率获得二甲基类似物。乙烯络合物的循环伏安图显示出不可逆的双电子氧化波，其电位明显低于五甲基二茂钌或钌二茂钌的电位。用对苯醌âBF3Â-OEt2 对这些络合物进行双电子化学氧化，得到了稳定的二阳离子（µ-Î-6â¶-6-五富勒烯）二钌络合物，产率适中。通过 X 射线衍射测定了五种络合物的分子结构。

  DOI：

  10.1039/a801941j
• 作为产物：
  描述：

  {(C5Me5)Ru(η5-C5H4CH(OO-t-Bu)CH3)} 以 氘代苯 为溶剂， 以90%的产率得到(η5-pentamethylcyclopentadienyl)(η5-acetylcyclopentadienyl)ruthenium(II)
  参考文献：
  名称：

  Carbon-carbon bond cleavage and skeletal rearrangement of coordinated norbornadiene. Preparation of a η6-6-methylfulvene complex [(C5Me5)Ru(C5H4CHCH3)]BF4

  摘要：

  The reaction of (C5Me5)Ru(nbd)Cl (1) (nbd = norbornadiene) with AgBF4 in ethanol yields [(C5Me5)Ru(nbd)(BF4) (2a), which undergoes skeletal rearrangement of the coordinated norbornadiene initiated by C(1)-C(2) bond cleavage to form a 6-methylfulvene complex [(C5Me5)Ru(C5H4CHCH3)](BF4) (3) upon stirring in dichloromethane. Complex 3 is directly derived from 1 by the treatment with AgBF4 in non-coordinating solvent such as CH2Cl2. Treatment of 3 with t-BuOOLi followed by pyrolysis affords an acetylruthenocene complex (C5Me5)Ru(C5H4COCH3) (5) by way Of (C5Me5)Ru[C5H4CH(OOtBu)CH3] (4). The molecular structure of 2b is determined by an X-ray diffraction study.

  DOI：

  10.1016/0022-328x(94)80130-4

文献信息

• Preparation, electrochemical oxidation, and XPS studies of unsymmetrical ruthenocenes bearing the pentamethylcyclopentadienyl ligand
  作者：Paul G. Gassman、Charles H. Winter

  DOI：10.1021/ja00226a030

  日期：1988.8

  La reaction d'oligomere du dichloro(pentamethylcyclopentadienyl) ruthenium(III) avec des sels de metaux alcalins d'une variete de derives cyclopentadienyles fournit une voie d'acces a des ruthenocenes non symetriques

  La 反应 d'oligomere du dichloro(pentamethylcyclopentadienyl) ruthenium(III) avec des sels de metaux alcalins d'une variete de衍生的环戊二烯基化合物fournit une voie d'acces a des rut​​henocenes non symetriques
• 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]
  作者：Masaru Sato、Yasushi Kawata、Hitoshi Shintate、Yoichi Habata、Sadatoshi Akabori、Kei Unoura

  DOI：10.1021/om960732t

  日期：1997.4.1

  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)Rumu-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)Rumu-eta(5):eta(1)-C5H4CH=C}Ru(PPh3)(2)(eta(5)-C5R5)](2+) by an intramolecular hydrogen transfer in 59% yield.