[CoCl2(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)] | 481050-30-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [CoCl2(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)]
• 英文别名: dichlorocobalt;4,11-dimethyl-1,4,8,11-tetrazabicyclo[6.6.2]hexadecane
• CAS: 481050-30-0
• 化学式: C₁₄H₃₀Cl₂CoN₄
• 分子量: 384.318
• InChiKey: HUTBWGOLSBMBKF-UHFFFAOYSA-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：

  ammonium hexafluorophosphate 、 [CoCl2(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)] 在 HCl 、 air 作用下， 以 甲醇 、 水 为溶剂， 生成 [CoCl2(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)](PF6)
  参考文献：
  名称：

  Synthesis, characterization, and X-ray crystal structures of cobalt(II) and cobalt(III) complexes of four topologically constrained tetraazamacrocycles

  摘要：

  The high spin Co2+ complexes of 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (1), 4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane (2), 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (3), and racemic-4,5,7,7,11,12,14,14-octamethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (4) have been synthesized and characterized by X-ray crystallography. The Co(III) complexes of 1-3 were also prepared by the chemical oxidation of the Co(II) complexes. The X-ray crystal structures of Co(1)Cl-2, Co(3)Cl-2, and [Co(3)Cl-2]PF6 demonstrate that the ligands enforce a distorted octahedral geometry on Co(II) and Co(III) with two cis sites occupied by chloro ligands. In contrast, the Co(II) complex of 4 is five-coordinate with trigonal bipyramidal geometry. The methyl groups substituted on the carbon atoms of ligand 4 define a shallow cavity, allowing only one chloride ligand to bind to the chelated metal ion. This difference in coordination geometry causes Co(4)Cl+ to be much more difficult to oxidize (E-1/2 = 1.176 V vs. SHE) than the octahedral Co(II) complexes of 1-3 (E-1/2 from -0.157 to 0.173 V vs. SHE). The Co(III) complexes of 1-3 have three absorbances in their electronic spectra, while typical cis-Co(III)N4X2 complexes have only two. This additional splitting of energy states is attributed to the increased distortion from octahedral resulting from the short ethylene cross-bridge on the macrobicyclic ligands. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01080-0
• 作为产物：
  描述：

  4,11-dimethyl-1,4,8,11-tetraaza-bicyclo[6.6.2]hexadecane 、 cobalt(II) chloride 以 乙腈 为溶剂， 生成 [CoCl2(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)]
  参考文献：
  名称：

  Synthesis, characterization, and X-ray crystal structures of cobalt(II) and cobalt(III) complexes of four topologically constrained tetraazamacrocycles

  摘要：

  The high spin Co2+ complexes of 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (1), 4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane (2), 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (3), and racemic-4,5,7,7,11,12,14,14-octamethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (4) have been synthesized and characterized by X-ray crystallography. The Co(III) complexes of 1-3 were also prepared by the chemical oxidation of the Co(II) complexes. The X-ray crystal structures of Co(1)Cl-2, Co(3)Cl-2, and [Co(3)Cl-2]PF6 demonstrate that the ligands enforce a distorted octahedral geometry on Co(II) and Co(III) with two cis sites occupied by chloro ligands. In contrast, the Co(II) complex of 4 is five-coordinate with trigonal bipyramidal geometry. The methyl groups substituted on the carbon atoms of ligand 4 define a shallow cavity, allowing only one chloride ligand to bind to the chelated metal ion. This difference in coordination geometry causes Co(4)Cl+ to be much more difficult to oxidize (E-1/2 = 1.176 V vs. SHE) than the octahedral Co(II) complexes of 1-3 (E-1/2 from -0.157 to 0.173 V vs. SHE). The Co(III) complexes of 1-3 have three absorbances in their electronic spectra, while typical cis-Co(III)N4X2 complexes have only two. This additional splitting of energy states is attributed to the increased distortion from octahedral resulting from the short ethylene cross-bridge on the macrobicyclic ligands. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01080-0