W(CO)5(η2-hex-3-yne) | 94970-82-8

• 英文名称: W(CO)5(η2-hex-3-yne)
• 英文别名: W(CO)5(η2-3-hexyne)
• CAS: 94970-82-8
• 化学式: C₁₁H₁₀O₅W
• 分子量: 406.047
• InChiKey: IKJVJEYSHBKKLK-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：

  碳酸甲丙酯 、 W(CO)5(η2-hex-3-yne) 以 正庚烷 为溶剂， 以0%的产率得到W(CO)5(2-Mepy)
  参考文献：
  名称：

  Reactivity of the M-(η2-alkyne) bond [M=Cr, W]: A kinetic and DFT study

  摘要：

  The displacement of eta(2)-coordinated 1-hexyne and 3-hexyne by 2-picoline from the Cr(CO)(5), BzCr(CO)(2) and W(CO)(5) fragments was studied. For the Cr systems, the data is consistent with a dissociative mechanism of alkyne displacement from the metal center. For W(CO)(5)(eta(2)-1-hexyne), the alkyne displacement follows a largely associative mechanism. The bond dissociation enthalpies obtained from the kinetic analysis are in good agreement with the values obtained by detailed DFT calculations. The calculations indicate that the energy required for the steric reorganization of the alkyne ligand prior to binding with the metal is an important factor in the determination of the overall metal-(eta(2)-alkyne) bond strength. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2010.01.014
• 作为产物：
  描述：

  六羰基钨 、 3-己炔 以 正庚烷 为溶剂， 生成 W(CO)5(η2-hex-3-yne)
  参考文献：
  名称：

  Reactivity of the M-(η2-alkyne) bond [M=Cr, W]: A kinetic and DFT study

  摘要：

  The displacement of eta(2)-coordinated 1-hexyne and 3-hexyne by 2-picoline from the Cr(CO)(5), BzCr(CO)(2) and W(CO)(5) fragments was studied. For the Cr systems, the data is consistent with a dissociative mechanism of alkyne displacement from the metal center. For W(CO)(5)(eta(2)-1-hexyne), the alkyne displacement follows a largely associative mechanism. The bond dissociation enthalpies obtained from the kinetic analysis are in good agreement with the values obtained by detailed DFT calculations. The calculations indicate that the energy required for the steric reorganization of the alkyne ligand prior to binding with the metal is an important factor in the determination of the overall metal-(eta(2)-alkyne) bond strength. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2010.01.014

文献信息

• Photosubstitution of carbon monoxide in W(CO)6 by alkyne: NMR detection of thermally unstable alkyne tungsten(0) carbonyl complexes
  作者：Teresa Szymańska-Buzar、Krystyna Kern

  DOI：10.1016/s0022-328x(00)00865-2

  日期：2001.3

  The NMR method has been used for the identification and characterisation of the unstable terminal alkyne complexes [W(CO)(5)(eta (2)-HC=CR)], [W(CO)(4)(eta (2)-HC=CR)(2)], [W(CO)(eta (2)-HC=CR)(3)], and vinylidene derivatives [W(CO)(5)(C=CHR)] formed in photochemical reactions of W(CO)(6) and each of the alkynes HC=CH, HC=CMe and HC=CCMe3. The terminal alkyne carbonyl complexes formed after sequential substitution of CO by alkyne were shown to be involved in the cyclotrimerisation of alkynes to arenes, which were detected by NMR spectroscopy and GC-MS analysis in the photochemical reaction of W(CO)(6) and each terminal alkyne used. Benzene substitute adducts with W(CO)(3) moiety were also observed by NMR in the above reactions. (C) 2001 Elsevier Science B.V. All rights reserved.