Hex-1-en-D12 | 97797-43-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: Hex-1-en-D12
• 英文别名: Perdeuterio-hex-1-en；dodecadeuterio-hex-1-ene；Hexene-d12；1,1,2,3,3,4,4,5,5,6,6,6-dodecadeuteriohex-1-ene
• CAS: 97797-43-8
• 化学式: C₆H₁₂
• 分子量: 96.066
• InChiKey: LIKMAJRDDDTEIG-DINUNEQDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  6
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  乙烯-d4 在 tetrakis[3,5-bis(trifluoromethyl)phenyl]boric acid bis(diethyl ether) complex 、 (^tolPNP)Cr((o-C₆H₄CH₂)₂O)(Me) 作用下， 以 氯苯 为溶剂， 反应 0.02h， 生成 Hex-1-en-D12 、 1-octene-d16
  参考文献：
  名称：

  乙烯低聚反应中的同位素标记：解决1-辛烯与1-己烯选择性的问题†

  摘要：

  根据同位素标记实验评估确定乙烯四聚和三聚的决定选择性的机械步骤。基于共享的色环庚烷中间体而不是将色环戊烷或Cr形态进行C-C偶联成独立的三聚和四聚催化剂的机理与数据一致，包括观察到的1-辛烯选择性上限。

  DOI：

  10.1039/c8dt04509g

文献信息

• Arene substituted cyclopentadienyl complexes of Zr and Hf: preparation and evaluation as catalysts for ethylene trimerisation
  作者：James A. Suttil、David S. McGuinness、Stephen J. Evans

  DOI：10.1039/c000913j

  日期：——

  A range of ZrIV and HfIV complexes of arene-substituted cyclopentadienyl ligands have been prepared and tested in ethylene oligomerisation. The complexes prepared were designed to be precatalysts to active species which have been predicted, through theoretical studies, to lead to selective ethylene trimerisation. While there is evidence for selective 1-hexene formation in the liquid fraction with two of the complexes, the major product in each case is polyethylene. Mechanistic studies reveal that trimerisation products most likely arise through a metallacycle mechanism, whereas there is evidence to suggest that polyethylene if formed via an alternate mechanism.

  一系列含有芳烃取代环戊二烯配体的锆（ZrIV）和铪（HfIV）配合物已被制备并用于乙烯聚合反应的测试。这些配合物的设计目的是作为活性物种的前催化剂，这些活性物种通过理论研究被预测能够实现选择性的乙烯三聚反应。虽然在液相中有证据表明其中两个配合物选择性地形成了1-己烯，但在每种情况下，主要产品都是聚乙烯。机理研究表明，三聚产品很可能是通过金属环机制生成的，而有证据表明聚乙烯则是通过另一种机制形成的。
• Mechanism of Ethylene Dimerization Catalyzed by Ti(OR′)₄/AlR₃
  作者：James A. Suttil、David S. McGuinness

  DOI：10.1021/om3008508

  日期：2012.10.8

  Ti-alkoxide-based catalysts in combination with AlEt3 are responsible for the production of a significant proportion of the world's 1-butene supply, via the dimerization of ethylene. A metallacycle mechanism is normally presumed to operate with this system. However, despite its importance, the catalyst is not mechanistically well understood. The mechanism of dimerization has been studied through a series of C2H4/C2D4 co-oligomerization experiments and comparison of theoretical and experimental mass spectra. The results obtained show that the textbook metallacycle mechanism is most likely not responsible for dimerization with this catalyst. Instead, an excellent fit between the theoretical and experimental mass spectra is obtained when a conventional Cossee-type mechanism (insertion/beta-hydride elimination) is modeled. The formation of both the primary product 1-butene and the secondary reaction products (ethylene/1-butene co-dimers) is best explained by this mechanism.