RuCl(η⁵-indenyl)(PHCy₂)(PPh₃) | 870854-21-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: RuCl(η⁵-indenyl)(PHCy₂)(PPh₃)
• 英文别名: [RuCl(η5-indenyl)(HPCy2)(PPh3)]；[RuCl(η5-indenyl)(triphenylphosphine)(dicyclohexylphosphine)]；[Ru(η5-indenyl)Cl(HP(C6H11)2)(PPh3)]；Ru(η5-indenyl)(PPh3)(PHCy2)Cl；dicyclohexylphosphane;1H-inden-1-ide;ruthenium(2+);triphenylphosphane;chloride
• CAS: 870854-21-0
• 化学式: C₃₉H₄₅ClP₂Ru
• 分子量: 712.257
• InChiKey: VOESCGMEPCPTFE-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  7.34
• 重原子数：
  43
• 可旋转键数：
  5
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  丙烯腈 、 RuCl(η⁵-indenyl)(PHCy₂)(PPh₃) 在 potassium tert-butylate 作用下， 以 甲苯 为溶剂， 反应 18.0h， 以66%的产率得到
  参考文献：
  名称：

  Inner- and Outer-Sphere Roles of Ruthenium Phosphido Complexes in the Hydrophosphination of Alkenes

  摘要：

  An inner-sphere synthetic cycle for the hydrophosphination of alkenes is proposed, based on observed [2 + 2] cydoaddition of a wide range of alkenes at a coordinatively unsaturated Ru=PR2 complex. Key intermediates in the cycle were prepared, and their reactions with various organic acid/base pairs were examined to identify both new ruthenium precursors and base cocatalysts that allow turnover of the proposed cycle. Two new cationic ruthenium indenyl phosphine complexes were isolated and structurally characterized. Although preliminary screening studies show the moderate activity of these and related neutral phosphido complexes for catalytic hydrophosphination of acrylonitrile by both HPPh2 and HPCy2, and comparable activity for the hydrophosphination of tert-butyl acrylate by HPPh2, no activity was observed for the analogous hydrophosphination of 1-hexene. This is attributed to strong binding of the substrate phosphine to the unsaturated, planar Ru=PR2 fragment generated in situ, which inhibits the innersphere, alkene cydoaddition mechanism. An alternative, outer-sphere Michael addition process, involving a saturated complex with a strongly nudeophilic pyramidal Ru-PR2 ligand, is proposed to rationalize the observed selectivity for catalytic hydrophosphination of activated, but not simple, alkenes. Implications for further catalyst development are discussed.

  DOI：

  10.1021/acs.organomet.5b00835
• 作为产物：
  描述：

  [Ru(η5-indenyl)(PCy2)(PPh3)]*0.25(pentane) 、 三乙基铵碘化物 以 二氯甲烷-D2 为溶剂， 生成 RuCl(η⁵-indenyl)(PHCy₂)(PPh₃)
  参考文献：
  名称：

  A Highly Reactive Ruthenium Phosphido Complex Exhibiting Ru−P π-Bonding

  摘要：

  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.

  DOI：

  10.1021/om0700056

文献信息

• Ruthenated Acetonitrile: Unusual Brønsted Acidity of a Polar “Aprotic” Solvent
  作者：Eric J. Derrah、Karina E. Giesbrecht、Robert McDonald、Lisa Rosenberg

  DOI：10.1021/om800343x

  日期：2008.10.13

  benzonitrile and pyridine adducts, suggest that the metalation of acetonitrile by 1 proceeds via an intermolecular C−H addition across the Ru═P double bond, rather than the intramolecular C−H activation of N-bound acetonitrile. This is confirmed by the observation, by 31P1H} NMR, of multiple product isotopomers in the reaction of 1 with a 1:1 mixture of d3- and d0-acetonitrile. O-Donor solvents also deprotonated

  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
• Electronic Control of Conformation in Mixed-Phosphine Complexes of the Ruthenium η⁵-Indenyl Fragment
  作者：Eric J. Derrah、Jazmin C. Marlinga、Debbie Mitra、Dawn M. Friesen、Shaun A. Hall、Robert McDonald、Lisa Rosenberg

  DOI：10.1021/om050259w

  日期：2005.11.1

  The solid-state conformations of a series of new, mixed secondary and tertiary phosphine complexes of the general formula [Ru(η5-indenyl)Cl(PPh3)(HPR2)] have been shown to persist in solution, largely because of the electronic requirements of the ancillary η5-indenyl ligand in these complexes. The crystallographically observed conformations, with the indenyl benzo ring lying anti to the secondary phosphine

  一系列通式新，混合仲和叔膦复合物的固态的构象的[Ru（η 5 -茚基）氯（PPH 3）（HPR 2）]已显示在溶液中继续存在，因为在很大程度上，辅助η的电子要求5在这些配合物-茚基配体。的晶体学上观察到的构象，与茚基苯并环躺在抗跨越的Ru-η仲膦5 -茚基键，被诊断在从PPH化学位移差溶液3个中的信号低温限制性1 H和131 H NMR谱。这些构象通过制备类似的氢基复合物的改变不同钢琴凳腿的相对反式的影响，特别是调谐的[Ru（η 5 -茚基）H（PPH 3）（HPR 2）]，这导致结构与茚基苯并环抗氢化物配体。这些研究为配位仲膦相对于PPh 3的相当强的反式影响提供了证据。讨论了对次膦的辅助配体行为的影响。
• 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。
• 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.