diiodo-tetra-tert-butylhexaphosphapentaprismane

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: diiodo-tetra-tert-butylhexaphosphapentaprismane
• 英文别名: P6C4(tBu)4I2；2,4,6,9-Tetratert-butyl-7,10-diiodo-1,3,5,7,8,10-hexaphosphapentacyclo[4.4.0.02,5.03,9.04,8]decane；2,4,6,9-tetratert-butyl-7,10-diiodo-1,3,5,7,8,10-hexaphosphapentacyclo[4.4.0.02,5.03,9.04,8]decane
• 化学式: C₂₀H₃₆I₂P₆
• 分子量: 716.157
• InChiKey: BKIFXIFHXSERHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  diiodo-tetra-tert-butylhexaphosphapentaprismane 、 甲基锂 以 乙醚 为溶剂， 以61%的产率得到P₆C₄(tBu)4Me₂
  参考文献：
  名称：

  Opening “Jaws”: Functionalisation of the hexaphosphapentaprismane cage, P6C4Bu4, affording X2P6C4Bu4 (X = Me, I), crystal and molecular structures of X2P6C4Bu4 (X = Me, I) and [cis-PtCl2Me2P6C4Bu4]

  摘要：

  The hexaphosphapentaprismane cage, (P6C4Bu4)-Bu-t ("Jaws"), can be readily opened by reaction with iodine at room temperature to afford the di-iodo derivative (I2P6C4Bu4)-Bu-t which can be converted to the dimethyl derivative (Me2P6C4Bu4)-Bu-t by treatment with LiMe. (Me2P6C4Bu4)-Bu-t behaves as a bidentate ligand towards PtCl2. The molecular structures of all the new compounds have been determined by P-31 and/or Pt-195 NMR spectroscopy and single crystal X-ray diffraction studies. (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.09.002
• 作为产物：
  描述：

  tetra(tert-butyl)hexaphosphapentaprismane 以 四氢呋喃 为溶剂， 反应 1.0h， 以79%的产率得到diiodo-tetra-tert-butylhexaphosphapentaprismane
  参考文献：
  名称：

  Opening “Jaws”: Functionalisation of the hexaphosphapentaprismane cage, P6C4Bu4, affording X2P6C4Bu4 (X = Me, I), crystal and molecular structures of X2P6C4Bu4 (X = Me, I) and [cis-PtCl2Me2P6C4Bu4]

  摘要：

  The hexaphosphapentaprismane cage, (P6C4Bu4)-Bu-t ("Jaws"), can be readily opened by reaction with iodine at room temperature to afford the di-iodo derivative (I2P6C4Bu4)-Bu-t which can be converted to the dimethyl derivative (Me2P6C4Bu4)-Bu-t by treatment with LiMe. (Me2P6C4Bu4)-Bu-t behaves as a bidentate ligand towards PtCl2. The molecular structures of all the new compounds have been determined by P-31 and/or Pt-195 NMR spectroscopy and single crystal X-ray diffraction studies. (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.09.002

文献信息

• An Approach to Rigid, Optically Active Chelate Ligands with <i>C</i> ₂ Symmetry: Dialkylhexaphosphapentaprismanes
  作者：Christine Höhn、Irene Keller、Lars Rohwer、Frank W. Heinemann、Ulrich Zenneck

  DOI：10.1002/ejic.201300994

  日期：2013.11.12

  a highly rigid chelate cage ligand core have been designed on the basis of alkylated C2-symmetric tetra-tert-butylhexaphosphapentaprismanes R2P6C4tBu4. The ligands are accessible by substitution of the diiodo derivative I2P6C4tBu4 with Grignard and organyllithium reagents. Depending on the optical properties of the organyl group, racemic or diastereomeric dialkylhexaphosphapentaprismanes R2P6C4tBu4

  基于烷基化的 C2 对称四叔丁基六磷酸五棱柱 R2P6C4tBu4，设计了具有高刚性螯合笼配体核心的非对映体 Pd 和 Pt 配合物。配体可通过用格氏试剂和有机锂试剂取代二碘衍生物 I2P6C4tBu4 来获得。根据有机基团的光学性质，外消旋或非对映异构二烷基六磷酸五棱柱 R2P6C4tBu4 可以用合适的 PdII 或 PtII 前体配合物处理，形成中性方形平面顺式-[(R2P6C4tBu4)PdCl2] 和顺式-[(R2P6C4tBu)esPdCl2] 配合物分别。在反应混合物中也观察到单烷基化产物 RIP6C4tBu4，但在大多数情况下，作为 PdII 和 PtII 的螯合配体是无活性的。对于 R = (S)-2-甲基丁基，PdCl2 复合物的非对映异构体通过柱色谱和结晶有效分离，得到高达 >99% de 的两种非对映异构体，它们通过 NMR 和 CD 光谱以及 X 射线衍射分析进行