[RuCl(η5-indenyl)(HPPh2)(PPh3)] | 870854-22-1

• 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)(HPPh2)(PPh3)]
• 英文别名: [(η5-indenyl)Ru(PPh3)(PPh2H)Cl]；[RuCl(η5-indenyl)(triphenylphosphine)(diphenylphosphine)]；[Ru(η5-indenyl)Cl(PPh2H)(triphenylphosphine)]；diphenylphosphane;1H-inden-1-ide;ruthenium(2+);triphenylphosphane;chloride
• CAS: 870854-22-1
• 化学式: C₃₉H₃₃ClP₂Ru
• 分子量: 700.162
• InChiKey: CBGUVYMHEGRTLC-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.32
• 重原子数：
  43
• 可旋转键数：
  5
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  [RuCl(η5-indenyl)(HPPh2)(PPh3)] 在 (CH₃)3COK 作用下， 以 氘代甲苯 为溶剂， 生成 [Ru(η5-indenyl)(diphenylphosphido)(triphenylphosphine)]
  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
• 作为产物：
  描述：

  (η5-indenyl)ruthenium(bis(triphenylphosphine))chloride 、 二苯基膦 以 正己烷 、 二氯甲烷 为溶剂， 以84.7%的产率得到[RuCl(η5-indenyl)(HPPh2)(PPh3)]
  参考文献：
  名称：

  在钌的混合膦配合物构象的电子控制η 5 -茚基片段

  摘要：

  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。

  DOI：

  10.1021/om050259w

文献信息

• Benzonitrile Adducts of Terminal Diarylphosphido Complexes: Preparative Sources of “Ru═PR₂”
  作者：Marc-André M. Hoyle、Dimitrios A. Pantazis、Hannah M. Burton、Robert McDonald、Lisa Rosenberg

  DOI：10.1021/om200822e

  日期：2011.12.12

  ruthenium complexes in the presence of benzonitrile yields stable, isolable nitrile adducts of the formula [Ru(η5-indenyl)(PAr2)(NCPh)(PPh3)], in which the terminal phosphido ligand is pyramidal at P and contains a stereochemically active lone pair. Unlike the analogous carbonyl adducts [Ru(η5-indenyl)(PAr2)(CO)(PPh3)], these benzonitrile complexes behave as masked sources of the highly reactive planar

  在苄腈的产率稳定存在次级二芳基膦钌络合物的脱卤化氢，式的[Ru（η的可分离腈加合物5 -茚基）（PAR 2）（NCPH）（PPH 3）]，其中，所述终端膦配位体是在锥体P和含有立体化学活性的孤对。不同于类似的羰基的加合物的[Ru（η 5 -茚基）（PAR 2）（CO）（PPH 3）]，这些苄腈配合物表现为高反应性的平面膦配合物的[Ru（η的掩蔽源5 -茚基）（PAR 2）（PPH 3）]，它包含一个Ru═PAR 2π键。苯甲腈加合物与二氢，甲基碘和1-己烯的加成（或环加成）反应，以及通过PPh 3配体的正金属化进行热分解，可以说明这一点。CO的焓从VS NCPH解离的[Ru（η 5 -茚基）（PR 2）（PPH 3）]片段（R =烷基，芳基）已经被计算，如具有添加H的轨迹2至模型平面膦配合物的[Ru（η 5 -茚基）（PME 2）（PME 3）]。后者的研究表明一个η的中间性2 -H 2加成物，的[Ru（η
• Inner- and Outer-Sphere Roles of Ruthenium Phosphido Complexes in the Hydrophosphination of Alkenes
  作者：Roman G. Belli、Krista M. E. Burton、Stephanie A. Rufh、Robert McDonald、Lisa Rosenberg

  DOI：10.1021/acs.organomet.5b00835

  日期：2015.12.14

  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.