cis,trans,cis-[Rh(H)2(PPh3)2(MeOH)2]PF6 | 505048-61-3

• 英文名称: cis,trans,cis-[Rh(H)2(PPh3)2(MeOH)2]PF6
• 英文别名: cis,trans,cis-[Rh(H)2(PPh3)2(methanol)2][PF6]
• CAS: 505048-61-3
• 化学式: C₃₈H₄₀O₂P₂Rh*F₆P
• 分子量: 838.552
• InChiKey: FOYWNTPDJAHNBG-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：

  cis,trans,cis-[Rh(H)2(PPh3)2(MeOH)2]PF6 、 N-苄烯丁胺 以 甲醇 为溶剂， 生成 cis-[Rh(PPh3)2(PhCH2N=CHPh)(PhCH2NH2)]PF6
  参考文献：
  名称：

  Imine Hydrolysis and Role of a Rhodium(I)−Imine−Amine Complex in Homogeneous H₂-Hydrogenation of the Imine and a Rare Example of Inequivalent NH₂ Protons

  摘要：

  A Rh-catalyzed, homogeneous hydrogenation of the imine, PhCH2N=CHPh, is shown to involve a Rh-imine-amine species that subsequently activates H-2, the amine (benzylamine) being formed via a Rh-catalyzed hydrolysis of the imine by adventitious water. The imine-amine complex, cis-{Rh[P(p-tolyl)(3)](2)(PhCH2N=CHPh)(NH2CH2Ph)}PF6 (2b), is structurally characterized, and the solution H-1 NMR data reveal inequivalent NH2 protons.

  DOI：

  10.1021/ic040037a
• 作为产物：
  描述：

  甲醇 、 氢气 、 (1,5-环辛二烯)二(三苯基膦)六氟磷酸铑二氯甲烷络合物(1:1) 以 甲醇 为溶剂， 生成 cis,trans,cis-[Rh(H)2(PPh3)2(MeOH)2]PF6
  参考文献：
  名称：

  Amine Products and Catalyst Poisoning in the Homogeneous H₂ Hydrogenation of Imines Catalyzed by the [Rh(COD)(PPh₃)₂]PF₆ Precursor

  摘要：

  The H-2 hydrogenations of PhN=CHPh and PhCH2N=CHPh are catalyzed by the precursor [Rh(COD)(PPh3)(2)]PF6. However, the amine product PhNHCH2Ph poisons the catalyst by coordination to the Rh through an arene moiety, while the other amine product, (PhCH2)(2)NH, forms a labile N-bonded species that does not poison the catalyst system.

  DOI：

  10.1021/om020992c

文献信息

• Catalyst poisoning in catalyzed imine hydrogenation: A novel zwitterionic Rh(I)/o-hydroxy-substituted imine complex
  作者：Paolo Marcazzan、Brian O. Patrick、Brian R. James

  DOI：10.1016/j.molcata.2006.04.012

  日期：2006.9

  During investigation of the homogeneous H-2-hydrogenation of the ketimine (o-HOC6H4)C(Me)=NCH2Ph catalyzed by the [Rh(COD)(PPh3)(2)]PF6 precursor in MeOH at ambient conditions, we have isolated [Rheta(4)-(C6H4O)C(-)(Me)=N(+)(H)CHPh}(PPh3)(2)]PF6 (3), an unusual zwitterionic Rh complex in which the imine is coordinated via the C-4 part of the o-hydroxy-arene moiety in a quinoid form; this tautomer is generated via proton transfer from the O-atom to the N-atom within the molecular, benzenoid form. Precipitation of 3 from the MeOH solution, even under H-2, causes sequestration of the Rh and complete suppression of the catalytic activity. (In a previously studied system with the corresponding, non-hydroxy-substituted ketimine, PhC(Me) = NCH2Ph, the Rh was sequestered as an inactive o-metalated species). The solid state structure of 3 is retained in CH2Cl2 solution, but in MeOH and Me2CO reversible loss of the ketimine generates the cis-[Rh(PPh3)(2)(solvent)(2)]PF6 species. (c) 2006 Elsevier B.V. All rights reserved.