[Rh(CO)(PPh3)3][K(18-crown-6)] | 1370085-01-0

• 英文名称: [Rh(CO)(PPh3)3][K(18-crown-6)]
• CAS: 1370085-01-0
• 化学式: C₁₂H₂₄O₆*C₅₅H₄₅OP₃Rh*K
• 分子量: 1221.21
• InChiKey: SDQHRSJQBDRWOF-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：

  [Rh(CO)(PPh3)3][K(18-crown-6)] 、 以 四氢呋喃 、 氘代四氢呋喃 为溶剂， 生成 三(三苯基膦)羰基氢化铑 、 [(o-(Ph2P)C6H4)3B]Rh(CO)[K(18-crown-6)]
  参考文献：
  名称：

  Synthesis of Iridaboratranes Bearing Phosphine-Tethered Borane: Reversible CO/PR₃ (R = Me, OMe, OEt) Substitution Reactions Induced by a σ-Electron-Acceptor Borane Ligand

  摘要：

  The iridaboratrane [{o-(Ph2P)C6H4}(3)B]IrH(CO) (1-Ir), bearing phosphine-tethered borane, was synthesized via phosphine ligand exchange between the tris(triphenylphosphine) carbonyl hydride IrH(CO)(PPh3)(3) (2-Ir) and the tris(phosphine)borane {o-(Ph2P)C6H4}(3)B (3). 1-Ir was fully characterized on the basis of its H-1, B-11, and P-31 NMR spectra, X-ray diffraction analysis, and elemental analysis. Density functional theory calculations revealed the important properties of the a-acceptor borane ligand that led to its unique electron distribution in 1-Ir. The borane ligand extracts a significant amount of electron density from the iridium center, but the iridium center maintains an electron density similar to that of the boron-free compound 2-Ir by decreasing pi back-donation from Ir to CO and strengthening the donation from the phosphorus atom (or by weakening the d(metal)-sigma*(P-R) interaction). The properties of the borane ligand can promote the reversible CO/PR3 (R = Me, OMe, OEt) substitution reaction.

  DOI：

  10.1021/om300216g
• 作为产物：
  描述：

  三(三苯基膦)羰基氢化铑 、 18-冠醚-6 、 potassium hydride 以 四氢呋喃 为溶剂， 以50%的产率得到[Rh(CO)(PPh3)3][K(18-crown-6)]
  参考文献：
  名称：

  Synthesis of Rhodaboratranes Bearing Phosphine-Tethered Boranes: Evaluation of the Metal–Boron Interaction

  摘要：

  A series of rhodaboratranes [{o(Ph2P)-C6H4}(3)BRhHn(CO)](m) (1, n = 1, m = 0; 4, n = 0, m = +1; 5, n = 0, m = -1) with different electron charges ranging from -1 to +1 have been synthesized. X-ray diffraction, IR, NMR, and DFT calculation studies have demonstrated that the sigma-acceptor borane ligand produces a unique electron distribution in these systems and significantly weakens the Rh-L bond (L = CO, PR3) trans to the boron. The reversible CO/PR3 (R = Me or Ph) substitution reactions of 1 and 5 are attributed to these properties.

  DOI：

  10.1021/om3000423