[ruthenium(η5-indenyl)(PPh3)(P(Cy)2)] | 934199-81-2

• 英文名称: [ruthenium(η5-indenyl)(PPh3)(P(Cy)2)]
• 英文别名: [Ru(η5-indenyl)(P(C6H11)2)(PPh3)]；[Ru(η5-indenyl)(PCy2)(PPh3)]；Ru(η5-indenyl)(PPh3)(PCy2)
• CAS: 934199-81-2
• 化学式: C₃₉H₄₄P₂Ru
• 分子量: 675.796
• InChiKey: KUOGERMXWHUDCD-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：

  [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
• 作为产物：
  描述：

  [Ru(η5-indenyl)(pyridine)(HP(C6H11)2)(PPh3)] 以 氘代甲苯 为溶剂， 生成 [ruthenium(η5-indenyl)(PPh3)(P(Cy)2)]
  参考文献：
  名称：

  钌乙腈：极性“非质子”溶剂的不寻常布朗斯台德酸度

  摘要：

  加入乙腈至复杂的[Ru（η 5 -茚基）（PR 2）（PPH 3）]（1）给出了不寻常的金属化产物的[Ru（η 5 -茚基）（CH 2 CN）（HPR 2）（PPH 3）]（2），其已在结构上进行了表征。该反应清楚地表明在1的末端磷酸配体上具有很高的布朗斯台德碱度。31 p { 1个H} NMR研究表明，较低的酸性N-供体的溶剂简单地破坏在RU-Pπ键1，得到的加合物的[Ru（η 5 -茚基）（L）（HPR 2）（PPH 3）]（L =苄腈（6）或吡啶（7）），这是处于平衡1和自由L的类似乙腈加合物（4）的形成过程中，在240 K内由NMR中观察到2，但快速更换在较高温度下降低2倍。替代路线向金属化的络合物的NMR研究2中，从阳离子N-结合乙腈加合物开始的[Ru（η 5 -茚基）（NCCH 3）（HPCY 2）（PPH 3）] [PF 6 ]（3A），以及已证明的苄腈和吡啶加合物的不稳定性

  DOI：

  10.1021/om800343x

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。