[(4-(4-octyloxyphenyl)-2,6-diphenylpyridine)Pt(Cl)(dimethylsulfoxide)] | 263755-53-9

• 英文名称: [(4-(4-octyloxyphenyl)-2,6-diphenylpyridine)Pt(Cl)(dimethylsulfoxide)]
• CAS: 263755-53-9
• 化学式: C₃₃H₃₈ClNO₂PtS
• 分子量: 743.269
• InChiKey: VCZAFABSWVRLFQ-UHFFFAOYSA-M

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：

  [(4-(4-octyloxyphenyl)-2,6-diphenylpyridine)Pt(Cl)(dimethylsulfoxide)] 、 一氧化碳 以 二甲基亚砜 为溶剂， 生成 cis-[(4-(4-octyloxyphenyl)-2,6-diphenylpyridine)Pt(Cl)(CO)]
  参考文献：
  名称：

  C−H Activation Induced by Water. Monocyclometalated to Dicyclometalated:  C∧N∧C Tridentate Platinum Complexes

  摘要：

  Metalation of 2,6-diphenylpyridine (1) by potassium tetrachloroplatinate in acetic acid gives a monocyclometalated chloride-bridged dimer 4. This dimer is split with CO to give a kinetic product st with the incoming CO trans to the orthometalated carbon. The kinetic product of cleavage is shown to be 16 kJ mol(-1) higher in energy than the thermodynamic product 9c, which has the CO trans to the pyridine nitrogen. The isomerization of 9t to 9c is shown not to take place via an associative mechanism and, with analogue 11, is effectively suppressed when excess chloride is added, implying that it takes place via a chloride dissociation. The monocyclometalated 9 undergoes a second cyclometalation to give the C boolean AND N boolean AND C dicyclometalated complex 15 in high yield. This second cyclometalation is brought about by the simple expedient of adding water to the monocyclometalated precursor. The addition of water is rationalized on the basis of needing to ionize the HCl byproduct of the reaction. Using a substituted pyridine (5) analogous chemistry is observed. Single-crystal X-ray structures of one of the intermediates (6) and one of the final products (15) have been solved. Density functional theory calculations are used to rationalize the isomerizations of the monocyclometalated intermediates and the need to ionize HCl in the second cyclometalation.

  DOI：

  10.1021/om9910423
• 作为产物：
  描述：

  4-(4'-octyloxyphenyl)-2,6-diphenylpyridine 以 氘代氯仿 、 溶剂黄146 、 二甲基亚砜 为溶剂， 生成 [(4-(4-octyloxyphenyl)-2,6-diphenylpyridine)Pt(Cl)(dimethylsulfoxide)]
  参考文献：
  名称：

  C−H Activation Induced by Water. Monocyclometalated to Dicyclometalated:  C∧N∧C Tridentate Platinum Complexes

  摘要：

  Metalation of 2,6-diphenylpyridine (1) by potassium tetrachloroplatinate in acetic acid gives a monocyclometalated chloride-bridged dimer 4. This dimer is split with CO to give a kinetic product st with the incoming CO trans to the orthometalated carbon. The kinetic product of cleavage is shown to be 16 kJ mol(-1) higher in energy than the thermodynamic product 9c, which has the CO trans to the pyridine nitrogen. The isomerization of 9t to 9c is shown not to take place via an associative mechanism and, with analogue 11, is effectively suppressed when excess chloride is added, implying that it takes place via a chloride dissociation. The monocyclometalated 9 undergoes a second cyclometalation to give the C boolean AND N boolean AND C dicyclometalated complex 15 in high yield. This second cyclometalation is brought about by the simple expedient of adding water to the monocyclometalated precursor. The addition of water is rationalized on the basis of needing to ionize the HCl byproduct of the reaction. Using a substituted pyridine (5) analogous chemistry is observed. Single-crystal X-ray structures of one of the intermediates (6) and one of the final products (15) have been solved. Density functional theory calculations are used to rationalize the isomerizations of the monocyclometalated intermediates and the need to ionize HCl in the second cyclometalation.

  DOI：

  10.1021/om9910423