syn-[ruthenium(η5-indenyl)(PPh3)(P(Cy)2CH2CH(nBu)] | 1231736-41-6

• 英文名称: syn-[ruthenium(η5-indenyl)(PPh3)(P(Cy)2CH2CH(nBu)]
• CAS: 1231736-41-6；1232773-69-1
• 化学式: C₄₅H₅₆P₂Ru
• 分子量: 759.957
• InChiKey: QQLHYNYFDHONIZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  syn-[ruthenium(η5-indenyl)(PPh3)(P(Cy)2CH2CH(nBu)] 、 2,6-二甲基吡啶盐酸盐(1:1) 以 氘代氯仿 为溶剂， 反应 24.0h， 生成
  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：

  1-己烯 、 RuCl(η⁵-indenyl)(PHCy₂)(PPh₃) 在 potassium tert-butylate 作用下， 以 甲苯 为溶剂， 反应 18.0h， 以65%的产率得到syn-[ruthenium(η5-indenyl)(PPh3)(P(Cy)2CH2CH(nBu)]
  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

• 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。