1,7-bis(3-pyridyl)octamethyltetrasiloxane | 1242280-37-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1,7-bis(3-pyridyl)octamethyltetrasiloxane
• 英文别名: [Dimethyl(pyridin-3-yl)silyl]oxy-[[dimethyl(pyridin-3-yl)silyl]oxy-dimethylsilyl]oxy-dimethylsilane；[dimethyl(pyridin-3-yl)silyl]oxy-[[dimethyl(pyridin-3-yl)silyl]oxy-dimethylsilyl]oxy-dimethylsilane
• CAS: 1242280-37-0
• 化学式: C₁₈H₃₂N₂O₃Si₄
• 分子量: 436.806
• InChiKey: WAGDGZBISXCWPY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  53.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  氘代吡啶 、 1,7-bis(3-pyridyl)octamethyltetrasiloxane 、 palladium diacetate 以 氘代甲苯 为溶剂， 生成 Pd(acetate)2(pyridine-d5)2
  参考文献：
  名称：

  Bis(pyridyl)siloxane Oligomeric Ligands for Palladium(II) Acetate: Synthesis and Binding Properties

  摘要：

  The complexation of a series of new bis(meia-pyridyl)methylsiloxane ligands with palladium(II) acetate in dilute toluene-d(8) solution was studied by (1)H NMR at 233-363 K, measuring the binding affinity and ring chain distribution as a function of ligand structure, temperature, and concentration. Significant differences in the ring distribution and Pd binding affinity were observed as a function of siloxane chain length, with hexa- and heptasiloxane spacers binding Pd most effectively. The (1)H NMR resonance of the singlet ortho aromatic proton was shifted unusually far downfield for the bidentate complex; the effect was strongest for the shortest chains and disappeared for chains with 10 or more siloxane units. Fitting the experimental data to a modified Jacobson-Stockmayer model demonstrated that the bidentate bis(pyridyl)siloxane complexes function as chelates in the concentration range 1-10 mM. Variable-temperature studies showed that all of the observed cyclic coordination oligomers are strainless. Therefore, entropic effects are implicated as the main cause of the observed trends in binding affinity, particularly the loss of conformational freedom of the siloxane chain upon binding.

  DOI：

  10.1021/om100316n
• 作为产物：
  描述：

  1,3-二氯-1,1,3,3,-四甲基二硅氧烷 、 3-pyridyldimethylsilanol 在 三乙胺 作用下， 以 氯仿 为溶剂， 反应 0.25h， 以39%的产率得到1,7-bis(3-pyridyl)octamethyltetrasiloxane
  参考文献：
  名称：

  Bis(pyridyl)siloxane Oligomeric Ligands for Palladium(II) Acetate: Synthesis and Binding Properties

  摘要：

  The complexation of a series of new bis(meia-pyridyl)methylsiloxane ligands with palladium(II) acetate in dilute toluene-d(8) solution was studied by (1)H NMR at 233-363 K, measuring the binding affinity and ring chain distribution as a function of ligand structure, temperature, and concentration. Significant differences in the ring distribution and Pd binding affinity were observed as a function of siloxane chain length, with hexa- and heptasiloxane spacers binding Pd most effectively. The (1)H NMR resonance of the singlet ortho aromatic proton was shifted unusually far downfield for the bidentate complex; the effect was strongest for the shortest chains and disappeared for chains with 10 or more siloxane units. Fitting the experimental data to a modified Jacobson-Stockmayer model demonstrated that the bidentate bis(pyridyl)siloxane complexes function as chelates in the concentration range 1-10 mM. Variable-temperature studies showed that all of the observed cyclic coordination oligomers are strainless. Therefore, entropic effects are implicated as the main cause of the observed trends in binding affinity, particularly the loss of conformational freedom of the siloxane chain upon binding.

  DOI：

  10.1021/om100316n

文献信息

• Bis(pyridyl)siloxane Oligomeric Ligands for Palladium(II) Acetate: Synthesis and Binding Properties
  作者：Michael N. Missaghi、John M. Galloway、Harold H. Kung

  DOI：10.1021/om100316n

  日期：2010.9.13

  The complexation of a series of new bis(meia-pyridyl)methylsiloxane ligands with palladium(II) acetate in dilute toluene-d(8) solution was studied by (1)H NMR at 233-363 K, measuring the binding affinity and ring chain distribution as a function of ligand structure, temperature, and concentration. Significant differences in the ring distribution and Pd binding affinity were observed as a function of siloxane chain length, with hexa- and heptasiloxane spacers binding Pd most effectively. The (1)H NMR resonance of the singlet ortho aromatic proton was shifted unusually far downfield for the bidentate complex; the effect was strongest for the shortest chains and disappeared for chains with 10 or more siloxane units. Fitting the experimental data to a modified Jacobson-Stockmayer model demonstrated that the bidentate bis(pyridyl)siloxane complexes function as chelates in the concentration range 1-10 mM. Variable-temperature studies showed that all of the observed cyclic coordination oligomers are strainless. Therefore, entropic effects are implicated as the main cause of the observed trends in binding affinity, particularly the loss of conformational freedom of the siloxane chain upon binding.