[RuCl(η5-indenyl)(HPCy2)(κ2-(o-C6H4)PPh2)] | 934199-95-8

• 英文名称: [RuCl(η5-indenyl)(HPCy2)(κ2-(o-C6H4)PPh2)]
• 英文别名: [ruthenium(η5-indenyl)(PPh2C6H4)(PH(Cy)2)]；Ru(η5-indenyl)(κ**(2)-o-C6H4PPh2)(PCy2H)
• CAS: 934199-95-8
• 化学式: C₃₉H₄₄P₂Ru
• 分子量: 675.796
• InChiKey: SPBXFPRSRFODGH-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)] 以 甲苯 为溶剂， 反应 18.0h， 生成 [RuCl(η5-indenyl)(HPCy2)(κ2-(o-C6H4)PPh2)]
  参考文献：
  名称：

  烯烃插入Ru-PR2键

  摘要：

  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.

  DOI：

  10.1021/acs.organomet.6b00757

文献信息

• The [2+2] cycloaddition of alkynes at a Ru–P π-bond
  作者：Eric J. Derrah、Robert McDonald、Lisa Rosenberg

  DOI：10.1039/c002765k

  日期：——

  The Ru[double bond, length as m-dash]P double bond in the 5-coordinate terminal phosphido complex [Ru(eta(5)-indenyl)(PR(2))(PPh(3))] undergoes regioselective [2+2] cycloaddition with simple and activated alkynes to give metallaphosphacyclobutene complexes. These unusual examples of alkyne insertion into a metal-heteroatom bond represent potentially important intermediates in stereoselective routes

  5配位末端磷酸酯络合物[Ru（eta（5）-茚基）（PR（2））（PPh（3））]中的Ru [双键，长度为m-P] P双键经历区域选择性[2 +2]与简单且活化的炔烃进行环加成反应，得到金属磷酰基环丁烯配合物。炔烃插入金属-杂原子键的这些不同寻常的例子代表了向新的膦试剂和配体的立体选择性途径中潜在的重要中间体。
• Concerted [2+2] Cycloaddition of Alkenes to a Ruthenium-Phosphorus Double Bond
  作者：Eric J. Derrah、Dimitrios A. Pantazis、Robert McDonald、Lisa Rosenberg

  DOI：10.1002/anie.201000356

  日期：2010.4.26

  A square deal for RuPR2: The RuPR2 π bond in a terminal phosphido complex undergoes regio‐ and stereoselective [2+2] cycloaddition reactions of alkenes to yield metallaphosphacyclobutanes (see structure; P red, Ru yellow, C gray), which are analogous to olefin metathesis intermediates.

  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。
• A Highly Reactive Ruthenium Phosphido Complex Exhibiting Ru−P π-Bonding
  作者：Eric J. Derrah、Dimitrios A. Pantazis、Robert McDonald、Lisa Rosenberg

  DOI：10.1021/om0700056

  日期：2007.3.1

  Multiple bonding in the terminal phosphido complex [Ru(PCy2)(eta(5)-indenyl)(PPh3)] (2a) is clearly demonstrated by solution, solid-state, and computational studies. Reactions of this dark blue, half-sandwich complex with CO, MeI, HNEt3Cl, HCl, NH4PF6, H-2, and Et3SiH demonstrate an unusual range of behavior resulting from combined coordinative unsaturation at Ru, high nucleophilicity/basicity of the phosphido P, and pi-character of the Ru-P interaction. The terminal, pi-bound phosphido structure is general for a range of PR2 species (R = Pr-i (2b), Ph (2c), Tol(p) (2d)). The very reactive diarylphosphido analogues 2c,d have been observed spectroscopically at low temperatures and can be trapped quantitatively as their CO adducts, [Ru(PAr2)(eta(5)-indenyl)(CO)(PPh3)] (3c,d), in which the Ru-P bond order is reduced to 1. Complex 2a and its analogue [Ru(PPr2i)(eta(5)-indenyl)(PPh3)] (2b) are consistently isolated with similar to 15% of their structural isomers, the ruthenium hydrido phosphaalkenes 9a, b, resulting from an apparent 1,2-H shift.