[Ru(η5-indenyl)(diphenylphosphido)(triphenylphosphine)] | 934199-96-9

• 英文名称: [Ru(η5-indenyl)(diphenylphosphido)(triphenylphosphine)]
• 英文别名: [RuCl(η5-indenyl)(PPh2)(PPh3)]
• CAS: 934199-96-9
• 化学式: C₃₉H₃₂P₂Ru
• 分子量: 663.701
• InChiKey: VQXMGGFNORCAFV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 氘代氯仿 为溶剂， 生成 [Ru(η5-indenyl)(diphenylphosphido)(triphenylphosphine)]
  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

文献信息

• 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.