[CoII(4,4′dmsalen)] | 14589-02-7

• 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: [CoII(4,4′dmsalen)]
• 英文别名: [Co^II(4,4′dmsalen)]；bis(5-methyl-salicylidene)-ethylenediamine-cobalt(II)
• CAS: 14589-02-7
• 化学式: C₁₈H₁₈CoN₂O₂
• 分子量: 353.346
• InChiKey: VCXPQDOBBOWMFW-BYCVLTJGSA-L

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：

  [CoII(4,4′dmsalen)] 在 双氧水 作用下， 生成
  参考文献：
  名称：

  钴（III）-硒离子催化的有机硫化物选择性H 2 O 2氧化为亚砜

  摘要：

  使用分光光度法研究了钴（II​​I）-salen离子催化的H 2 O 2选择性氧化为有机硫化物转化为亚砜的催化活性。催化反应通过Michaelis-Menten动力学进行，反应速率对底物以及Salen配体中存在的取代基的性质高度敏感。产物分析表明，芳基甲基硫化物被选择性地氧化成相应的亚砜。基于光谱和动力学研究，提出了两种可能的机理。

  DOI：

  10.1016/j.poly.2015.07.020
• 作为产物：
  描述：

  (N,N'-ethylenebis(5-methylsalicylideneaminato))mononitrosylcobalt(III) 以 solid 为溶剂， 生成 [CoII(4,4′dmsalen)]
  参考文献：
  名称：

  固相中亚硝酰基配合物的一氧化氮解离反应的热表征。具有混合配体四齿席夫碱的单亚硝基钴 (III) 络合物

  摘要：

  摘要 单亚硝基钴 (III) 在固相中的热解离反应，式为 CoL 4 NO（L 4 表示四齿配体，如 bzacen、salen 及其 5-NO 2 、5-Cl 和 5-Me 衍生物 2 ) 已通过 TG、DSC 和热解气相色谱分析进行了研究。这些配合物在 160-300°C 范围内每摩尔消除了 1 摩尔 NO，并重现了具有与真正的 CoL 4 配合物相似的 X 射线衍射图的 CoL 4 配合物。动力学分析表明NO的解离过程遵循一阶方程；活化焓值为 120–124 kJ mol -1 ，与 L 4 的性质无关。通过 DSC 方法测定的 NO 解离热值在 40-50 kJ mol -1 的范围内。根据这些热化学数据和 NO 的溶解热数据，计算出溶液中 NO 的解离能为 52-61 kJ mol -1 。根据 CoNO 键的性质讨论了热数据。

  DOI：

  10.1016/0040-6031(85)85400-9

文献信息

• A Novel Series of Co^III(salen-type) Complexes Containing a Seven-Membered Metallacycle: Synthesis, Structural Characterization and Factors Affecting the Metallacyclization Rate
  作者：Patrizia Siega、Renata Dreos、Giovanna Brancatelli、Ennio Zangrando、Claudio Tavagnacco、Višnja Vrdoljak、Tomica Hrenar

  DOI：10.1021/om401038v

  日期：2014.2.24

  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.
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Co: SVol.B1, 99, page 219 - 221
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