[CoIII(4,4′dmsalen)(py)2]ClO4 | 1555806-92-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [CoIII(4,4′dmsalen)(py)2]ClO4
• 英文别名: [Co^III(4,4′dmsalen)(py)₂]ClO₄
• CAS: 1555806-92-2
• 化学式: C₂₈H₂₈CoN₄O₂*ClO₄
• 分子量: 611.0
• InChiKey: APDHMZNAEBHDPQ-WCLOSASOSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  氯碘甲烷 、 [CoIII(4,4′dmsalen)(py)2]ClO4 在 sodium tetrahydroborate 、 sodium hydroxide 、 palladium dichloride 作用下， 以 甲醇 、 水 为溶剂， 反应 1.3h， 以53.9%的产率得到[Co^III(4,4′dmsalen)(CH₂Cl)]₂
  参考文献：
  名称：

  A Novel Series of Co^III(salen-type) Complexes Containing a Seven-Membered Metallacycle: Synthesis, Structural Characterization and Factors Affecting the Metallacyclization Rate

  摘要：

  A series of electronically tuned trans-[Co-III(chel)(CH2Cl)](2) complexes, where chel is a salen derivative (salen = 2,2'-ethylenebis(nitrilomethylidene)-diphenol) containing either two or four methyl substituents in different positions, has been synthesized and characterized, both in solution and in the solid state. These complexes undergo an intramolecular cyclization reaction in methanolic solution to form the corresponding cis beta organometallic derivative containing a seven-membered metallacycle, by replacement of the Cl atom of the axial CH2Cl by the salen phenolate oxygen. The cyclization rate increases on going from two to four methyl substituents in the chelate, in agreement with the electrochemical data that evidence a general shift toward more negative values with an increase in the number of methyl substituents. The cyclization rate is also affected by the substituent position, and both electrochemical and kinetic data evidence a remarkable influence of the methyls on the -C=N- groups of the chelate. The X-ray structures of cyclized complexes, (Co-III(chelCH(2))(py)(H2O)(+), show a dependence of the conformation of the seven-membered metallacycle on the different positions of substituents in the chelate. In fact, in the complex having methyls on the -C=N- groups, the conformation is characterized by having the methylene carbon atom significantly displaced (ca. 1.26 angstrom) from the aromatic ring plane, whereas in the complex lacking methyl groups in those positions, the atoms of the Ph-O-CH2 fragment are coplanar. The standard Gibbs energies obtained by quantum chemical calculation reveal that the different conformations observed in the solid state are mainly the result of the energetically unfavorable setup of the methyls on the -C=N- groups and of the energetically favorable displacement of the CH2 group out of plane of the aromatic ring. H-1 NMR data suggest that the different conformations of the metallacycle are, at least partially, retained in solution.

  DOI：

  10.1021/om401038v
• 作为产物：
  描述：

  吡啶 、 bis-(5-methyl-salicylidene)-ethylenediamine 、 sodium perchlorate 、 cobalt(II) diacetate tetrahydrate 在 氧气 作用下， 以 甲醇 、 水 为溶剂， 反应 3.0h， 以97.1%的产率得到[CoIII(4,4′dmsalen)(py)2]ClO4
  参考文献：
  名称：

  A Novel Series of Co^III(salen-type) Complexes Containing a Seven-Membered Metallacycle: Synthesis, Structural Characterization and Factors Affecting the Metallacyclization Rate

  摘要：

  A series of electronically tuned trans-[Co-III(chel)(CH2Cl)](2) complexes, where chel is a salen derivative (salen = 2,2'-ethylenebis(nitrilomethylidene)-diphenol) containing either two or four methyl substituents in different positions, has been synthesized and characterized, both in solution and in the solid state. These complexes undergo an intramolecular cyclization reaction in methanolic solution to form the corresponding cis beta organometallic derivative containing a seven-membered metallacycle, by replacement of the Cl atom of the axial CH2Cl by the salen phenolate oxygen. The cyclization rate increases on going from two to four methyl substituents in the chelate, in agreement with the electrochemical data that evidence a general shift toward more negative values with an increase in the number of methyl substituents. The cyclization rate is also affected by the substituent position, and both electrochemical and kinetic data evidence a remarkable influence of the methyls on the -C=N- groups of the chelate. The X-ray structures of cyclized complexes, (Co-III(chelCH(2))(py)(H2O)(+), show a dependence of the conformation of the seven-membered metallacycle on the different positions of substituents in the chelate. In fact, in the complex having methyls on the -C=N- groups, the conformation is characterized by having the methylene carbon atom significantly displaced (ca. 1.26 angstrom) from the aromatic ring plane, whereas in the complex lacking methyl groups in those positions, the atoms of the Ph-O-CH2 fragment are coplanar. The standard Gibbs energies obtained by quantum chemical calculation reveal that the different conformations observed in the solid state are mainly the result of the energetically unfavorable setup of the methyls on the -C=N- groups and of the energetically favorable displacement of the CH2 group out of plane of the aromatic ring. H-1 NMR data suggest that the different conformations of the metallacycle are, at least partially, retained in solution.

  DOI：

  10.1021/om401038v