η6,η5-bis(1,3-bis(trimethylsilyl)indenyl)(3,6-dithiaoctane)zirconium | 943912-13-8

• 英文名称: η6,η5-bis(1,3-bis(trimethylsilyl)indenyl)(3,6-dithiaoctane)zirconium
• CAS: 943912-13-8
• 化学式: C₃₆H₆₀S₂Si₄Zr
• 分子量: 760.57
• InChiKey: FAGRAHYQVJEUKR-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：

  η6,η5-bis(1,3-bis(trimethylsilyl)indenyl)(3,6-dithiaoctane)zirconium 以 甲苯 为溶剂， 生成 bis(η5-1,3-bis(trimethylsilyl)indenyl)bis(ethylthiolato)zirconium
  参考文献：
  名称：

  C-O和C-S键断裂在螯合二醚和硫醚由η推荐9，η 5 -双（茚基）合锆的夹心复合：一个组合的实验和计算研究

  摘要：

  Gently warming the eta(6),eta(5)-bis(indenyl)zirconium dimethoxyethane compound (eta(6)-C9H5-1,3-(SiMe3)(2))(eta(5)-C9H5-1,3-(SiMe3)(2))Zr(DME) (1-DME) to 45 degrees C resulted in C-O bond scission to yield an equimolar mixture of the zirconocene ethylene compound (eta(5)-C9H5-1,3-(SiMe3)(2))(2)Zr(eta(2)-CH2CH2) and the corresponding zirconium bis(methoxide) complex (eta(5)-C9H5-1,3-(SiMe3)(2))(2)Zr(OMe)(2). Monitoring the relative rates of 1-DME versus 1-DME-d(10) cleavage by H-1 NMR spectroscopy established no kinetic isotope effect (k(H)/k(D) = 1.0(1)), eliminating the possibility of C-H activation in or prior to the rate-determining step. Computational studies support a pathway involving rate-determining DME dissociation from the eta(6),eta(5)-bis(indenyl)zirconium complex followed by facile eta(6) to eta(5) indenyl haptotropic rearrangement and C-O bond scission. Corresponding C-S bond cleavage chemistry has been investigated for three thioethers and the mechanism of bond activation compared to the oxygen congeners.

  DOI：

  10.1021/om0701120
• 作为产物：
  描述：

  1,2-乙基乙烷 、 η9,η5-bis(1,3-bis(trimethylsilyl)indenyl)zirconium 以 氘代甲苯 为溶剂， 生成 η6,η5-bis(1,3-bis(trimethylsilyl)indenyl)(3,6-dithiaoctane)zirconium
  参考文献：
  名称：

  C-O和C-S键断裂在螯合二醚和硫醚由η推荐9，η 5 -双（茚基）合锆的夹心复合：一个组合的实验和计算研究

  摘要：

  Gently warming the eta(6),eta(5)-bis(indenyl)zirconium dimethoxyethane compound (eta(6)-C9H5-1,3-(SiMe3)(2))(eta(5)-C9H5-1,3-(SiMe3)(2))Zr(DME) (1-DME) to 45 degrees C resulted in C-O bond scission to yield an equimolar mixture of the zirconocene ethylene compound (eta(5)-C9H5-1,3-(SiMe3)(2))(2)Zr(eta(2)-CH2CH2) and the corresponding zirconium bis(methoxide) complex (eta(5)-C9H5-1,3-(SiMe3)(2))(2)Zr(OMe)(2). Monitoring the relative rates of 1-DME versus 1-DME-d(10) cleavage by H-1 NMR spectroscopy established no kinetic isotope effect (k(H)/k(D) = 1.0(1)), eliminating the possibility of C-H activation in or prior to the rate-determining step. Computational studies support a pathway involving rate-determining DME dissociation from the eta(6),eta(5)-bis(indenyl)zirconium complex followed by facile eta(6) to eta(5) indenyl haptotropic rearrangement and C-O bond scission. Corresponding C-S bond cleavage chemistry has been investigated for three thioethers and the mechanism of bond activation compared to the oxygen congeners.

  DOI：

  10.1021/om0701120