[ruthenium(η5-indenyl)(PPh3)(κ2-C2H4P(Cy)2)] | 1231736-40-5

• 英文名称: [ruthenium(η5-indenyl)(PPh3)(κ2-C2H4P(Cy)2)]
• CAS: 1231736-40-5
• 化学式: C₄₁H₄₈P₂Ru
• 分子量: 703.85
• InChiKey: KEDFLZYUJNXAIE-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

• 作为产物：
  描述：

  [ruthenium(η5-indenyl)(PPh3)(P(Cy)2)] 、 乙烯 以 not given 为溶剂， 以99%的产率得到[ruthenium(η5-indenyl)(PPh3)(κ2-C2H4P(Cy)2)]
  参考文献：
  名称：

  烯烃与钌-磷双键的协同[2 + 2]环加成反应

  摘要：

  方形成交为RuPR 2：本RuPR 2在终端膦络合物经历区域选择性和立体选择性的[2 + 2]环加成的烯烃，得到metallaphosphacyclobutanes的反应（见结构π键; p红色，黄色的Ru，C灰色），类似于烯烃复分解中间体。

  DOI：

  10.1002/anie.201000356

文献信息

• Alkene Insertions into a Ru–PR₂ Bond
  作者：Krista M. E. Burton、Dimitrios A. Pantazis、Roman G. Belli、Robert McDonald、Lisa Rosenberg

  DOI：10.1021/acs.organomet.6b00757

  日期：2016.12.12

  An unusually broad series of discrete alkene insertion reactions has provided the opportunity to examine the mechanism(s) of this fundamental carbon-heteroatom bond forming process. Ethylene, electron-rich and electron-poor (activated) alkenes all react with the Ru-P double bond in Ru(eta(5)-indenyl)(PCy2)(PPh3) to form kappa(2)-ruthenaphosphacyclobutanes. Thermal decomposition of these metallacycles in solution, via alkene deinsertion and beta-hydride elimination, is particularly favored for electron-rich alkenes, and hydride-containing decomposition products are implicit intermediates in the observed isomerization of 1-hexene. Kinetic studies, including a Hammett analysis of the insertion reactions of para-substituted styrenes, suggest that two distinct inner-sphere pathways operate for the insertion of electron-rich versus activated alkenes. DFT analyses have identified one pathway involving simple cycloaddition via a four-centered transition state and another that proceeds through an eta(2)-alkene intermediate. Such an intermediate was observed spectroscopically during formation of the ethylene metallacycle, but not for substituted alkenes. We propose that "pre-polarized", activated alkenes participate in direct cycloaddition, while rate determining eta(2)-adduct formation is necessary for the activation of electron-rich alkenes toward migratory insertion into the Ru-P bond.