cis-1,2-d2-dimethoxyethane | 943912-21-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-1,2-d2-dimethoxyethane
• 英文别名: cis-1,2-d2-DME
• CAS: 943912-21-8
• 化学式: C₄H₁₀O₂
• 分子量: 92.1063
• InChiKey: XTHFKEDIFFGKHM-BWYUKSRHSA-N

反应信息

• 作为反应物：
  描述：

  η9,η5-bis(1,3-bis(trimethylsilyl)indenyl)zirconium 、 cis-1,2-d2-dimethoxyethane 以 氘代苯 为溶剂， 生成 anti-η6,η5-bis(1,3-bis(trimethylsilyl)indenyl)(cis-1,2-d2-dimethoxyethane)zirconium 、 syn-η6,η5-bis(1,3-bis(trimethylsilyl)indenyl)(cis-1,2-d2-dimethoxyethane)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