Cr(CO)5(η2-1-hexyne) | 850805-12-8

• 英文名称: Cr(CO)5(η2-1-hexyne)
• CAS: 850805-12-8
• 化学式: C₁₁H₁₀CrO₅
• 分子量: 274.193
• InChiKey: PPKWTFFOWZSGGY-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  六羰基铬 、 1-己炔 以 正庚烷 为溶剂， 生成 Cr(CO)5(η2-1-hexyne)
  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

• Ultrafast Infrared Mechanistic Studies of the Interaction of 1-Hexyne with Group 6 Hexacarbonyl Complexes
  作者：Jennifer E. Shanoski、Christine K. Payne、Matthias F. Kling、Elizabeth A. Glascoe、Charles B. Harris

  DOI：10.1021/om049101m

  日期：2005.4.1

  ultrafast solvation and rearrangement dynamics following the photolysis of M(CO)6 (M = Cr, Mo, W) in terminal alkyne solutions have been investigated. Upon photoinitiated loss of a ligand from the parent metal hexacarbonyl, coordination to an alkyne solvent molecule is followed by rearrangement to a complex that is bound to the terminal alkyne site in a π-bonded fashion. This rearrangement occurs on a time

  M（CO）6光解后的超快溶剂化和重排动力学已经研究了末端炔烃溶液中的（M = Cr，Mo，W）。在从母体金属六羰基光引发配体丢失后，配位至炔烃溶剂分子，然后重排为以π键结合方式与末端炔烃位点结合的配合物。这种重排发生在与金属-配体结合能反相关的时间尺度上。对于该过程，排除了解离重排，有利于缔合或交换机制。审查了以前的理论和实验研究，我们得出的结论是，在环境温度下，在飞秒到毫秒级的范围内，从根本上无法达到亚乙烯基物质的最终重排。