cis-[Rh(PPh3)2(MeOH)2]PF6 | 728023-65-2

• 英文名称: cis-[Rh(PPh3)2(MeOH)2]PF6
• CAS: 728023-65-2
• 化学式: C₃₈H₃₈O₂P₂Rh*F₆P
• 分子量: 836.536
• InChiKey: XIBQSMRCWJVKME-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

• 作为反应物：
  描述：

  cis-[Rh(PPh3)2(MeOH)2]PF6 、 奥来替酚 以 甲醇 为溶剂， 以50%的产率得到[Rh(η-4-(C6H4O)C(CH3)N(H)CH2C6H5)(PPh3)2]PF6
  参考文献：
  名称：

  Catalyst poisoning in catalyzed imine hydrogenation: A novel zwitterionic Rh(I)/o-hydroxy-substituted imine complex

  摘要：

  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 [Rh{eta(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.

  DOI：

  10.1016/j.molcata.2006.04.012

文献信息

• 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
  作者：Paolo Marcazzan、Chalil Abu-Gnim、Kapila N. Seneviratne、Brian R. James

  DOI：10.1021/ic040037a

  日期：2004.8.1

  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.