(S)-(pent-1-en-3-yloxy)tris((tri-tert-butylsilyl)oxy)tantalum(V) hydride | 347370-42-7

• 分子结构分类: 有机化合物 - 有机金属化合物
• 英文名称: (S)-(pent-1-en-3-yloxy)tris((tri-tert-butylsilyl)oxy)tantalum(V) hydride
• CAS: 347370-42-7
• 化学式: C₄₁H₉₁O₄Si₃Ta
• 分子量: 913.376
• InChiKey: DGOBDLIJAFLIJV-LEOCAFOWSA-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：

  (S)-(pent-1-en-3-yloxy)tris((tri-tert-butylsilyl)oxy)tantalum(V) hydride 在 ethyl vinyl ketone 作用下， 以 氘代甲苯 为溶剂， 生成
  参考文献：
  名称：

  Insertion of H₂CCHX (X = F, Cl, Br, OⁱPr) into (^tBu₃SiO)₃TaH₂ and β-X-Elimination from (^tBu₃SiO)₃HTaCH₂CH₂X (X = OR):  Relevance to Ziegler−Natta Copolymerizations

  摘要：

  The insertion of H2C=CHX (X = OR; R = Me, Et, Pr-n,Pr-1, CH=CH2, Ph) into ((Bu3SiO)-Bu-t)(3)TaH2 (1) afforded ((Bu3SiO)-Bu-t)(3)HTaCH2CH2X (2-CH2CH2X), which beta -X-eliminated to give ethylene and ((Bu3SiO)-Bu-t)(3)- HTaX (3-X). beta -X-elimination rates were inversely proportional to the size of R. An X-ray crystallographic study of ((Bu3SiO)-Bu-t)(3)(HTaCH2CH2OBu)-Bu-t (2-(CH2CH2OBu)-Bu-t) revealed a distorted trigonal bipyramidal structure with an equatorial plane containing be hydride and a -(CH2CH2OBu)-Bu-t ligand with a staggered disposition. erythro and threo-((Bu3SiO)-Bu-t)(3)HTaCHDCHDOEt (2-CHDCHDOEt) are staggered in solution, according to H-1 NMR spectroscopic studies, and eliminated cis- and trans-HDC=CHD, respectively, helping verify the four-centered transition state for beta -OEt-elimination. When X = F, Cl, or Br, 2-CH2CH2X was not observed en route to 3-X, signifying that olefin insertion was rate-determining. Insertion rates suggested that substantial positive charge on the substituted carbon was incurred. The reactivity of other H2C=CHX with 1, and a discussion of the observations and their ramifications on the incorporation of functionalized monomers in Ziegler-Natta copolymerizations, are presented.

  DOI：

  10.1021/ja003315n
• 作为产物：
  描述：

  (silox)3TaH2 、 1-戊烯-3-酮 以 氘代甲苯 为溶剂， 生成 (S)-(pent-1-en-3-yloxy)tris((tri-tert-butylsilyl)oxy)tantalum(V) hydride
  参考文献：
  名称：

  Insertion of H₂CCHX (X = F, Cl, Br, OⁱPr) into (^tBu₃SiO)₃TaH₂ and β-X-Elimination from (^tBu₃SiO)₃HTaCH₂CH₂X (X = OR):  Relevance to Ziegler−Natta Copolymerizations

  摘要：

  The insertion of H2C=CHX (X = OR; R = Me, Et, Pr-n,Pr-1, CH=CH2, Ph) into ((Bu3SiO)-Bu-t)(3)TaH2 (1) afforded ((Bu3SiO)-Bu-t)(3)HTaCH2CH2X (2-CH2CH2X), which beta -X-eliminated to give ethylene and ((Bu3SiO)-Bu-t)(3)- HTaX (3-X). beta -X-elimination rates were inversely proportional to the size of R. An X-ray crystallographic study of ((Bu3SiO)-Bu-t)(3)(HTaCH2CH2OBu)-Bu-t (2-(CH2CH2OBu)-Bu-t) revealed a distorted trigonal bipyramidal structure with an equatorial plane containing be hydride and a -(CH2CH2OBu)-Bu-t ligand with a staggered disposition. erythro and threo-((Bu3SiO)-Bu-t)(3)HTaCHDCHDOEt (2-CHDCHDOEt) are staggered in solution, according to H-1 NMR spectroscopic studies, and eliminated cis- and trans-HDC=CHD, respectively, helping verify the four-centered transition state for beta -OEt-elimination. When X = F, Cl, or Br, 2-CH2CH2X was not observed en route to 3-X, signifying that olefin insertion was rate-determining. Insertion rates suggested that substantial positive charge on the substituted carbon was incurred. The reactivity of other H2C=CHX with 1, and a discussion of the observations and their ramifications on the incorporation of functionalized monomers in Ziegler-Natta copolymerizations, are presented.

  DOI：

  10.1021/ja003315n