Cp*W(O)2(CH2SiMe3) | 96760-75-7

• 英文名称: Cp*W(O)2(CH2SiMe3)
• 英文别名: (η5-C5H5)tungsten(dioxo)(CH2SiMe3)
• CAS: 96760-75-7
• 化学式: C₉H₁₆O₂SiW
• 分子量: 368.16
• InChiKey: JPLOOGQSBOVANK-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：

  Cp*W(O)2(CH2SiMe3) 在 H₂O₂ 作用下， 以 乙醚 、 水 为溶剂， 生成 Cp*W(O)(η2-O2)(CH2SiMe3)
  参考文献：
  名称：

  钼和钨的烷基二氧杂配合物中显着惰性的金属烷基键

  摘要：

  DOI：

  10.1021/om00098a033
• 作为产物：
  描述：

  (η5-C5H5)tungsten(nitrosyl)(CH2SiMe3)2 在 O₂ 作用下， 以 正己烷 为溶剂， 以65%的产率得到Cp*W(O)2(CH2SiMe3)
  参考文献：
  名称：

  新型的含钨的有机金属羰基配合物

  摘要：

  DOI：

  10.1021/om00127a033

文献信息

• New types of organometallic oxo complexes containing molybdenum and tungsten
  作者：Peter Legzdins、Everett C. Phillips、Luis Sanchez

  DOI：10.1021/om00106a013

  日期：1989.4
• Variable Pathways for Oxygen Atom Insertion into Metal–Carbon Bonds: The Case of Cp*W(O)₂(CH₂SiMe₃)
  作者：Jiajun Mei、Kurtis M. Carsch、Cody R. Freitag、T. Brent Gunnoe、Thomas R. Cundari

  DOI：10.1021/ja309755g

  日期：2013.1.9

  Cp*W(O)(2)(CH2SiMe3) (1) (Cp* = eta(5)-pentamethylcyclopentadienyl) reacts with oxygen atom donors (e.g., H2O2, PhIO, IO4-) in THF/water to produce TMSCH2OH (TMS = trimethylsilyl). For the reaction of 1 with IO4-, the proposed pathway for alcohol formation involves coordination of IO4- to 1 followed by concerted migration of the -CH2TMS ligand to the coordinated oxygen of IO4- with concomitant dissociation of IO3- to produce Cp*W(O)(2)(OCH2SiMe3) (3), which undergoes protonolysis to yield free alcohol. In contrast to the reaction with IO4-, the reaction of 1 with H2O2 results in the formation of the eta(2)-peroxo complex Cp*W(O)(eta(2)-O-2)(CH2SiMe3) (2). In the presence of acid (HCl) or base (NaOH), complex 2 produces TMSCH2OH. The conversion of 2 to TMSCH2OH catalyzed by Bronsted acid is proposed to occur through protonation of the eta(2)-peroxo ligand, which facilitates the transfer of the -CH2TMS ligand to a coordinated oxygen of the eta(2)-hydroperoxo ligand. In contrast, the hydroxide promoted conversion of 2 to TMSCH2OH is proposed to involve hydroxide coordination, followed by proton transfer from the hydroxide ligand to the peroxide ligand to yield a kappa(1)-hydroperoxide intermediate. The migration of the -CH2TMS ligand to the coordinated oxygen of the kappa(1)-hydroperoxo produces an alkoxide complex, which undergoes protonolysis to yield free alcohol.