[1-(2-mercapto-2-methylpropyl)-5-(2-thia-3,3-dimethylbutyl)-1,5-diazacyclooctanato]nickel(II) iodide complex | 284670-47-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• 英文名称: [1-(2-mercapto-2-methylpropyl)-5-(2-thia-3,3-dimethylbutyl)-1,5-diazacyclooctanato]nickel(II) iodide complex
• CAS: 284670-47-9
• 化学式: C₁₅H₃₁N₂NiS₂*I
• 分子量: 489.151
• InChiKey: DRYYBEJMWUKSDA-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：

  [1-(2-mercapto-2-methylpropyl)-5-(2-thia-3,3-dimethylbutyl)-1,5-diazacyclooctanato]nickel(II) iodide complex 在 CH₂Cl₂ 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 生成 [1-(2-mercapto-2-methylpropyl)-5-(2-thia-3,3-dimethylbutyl)-1,5-diazacyclooctanato]nickel(II) chloride dihydrate complex
  参考文献：
  名称：

  Correlation of electrochemistry, nucleophilicity and density functional calculations of the cis-dithiolate (bme*-daco)Ni

  摘要：

  Upon the sequential stoichiometric addition of methyl iodide to acetonitrile solutions of the square planar nickel (II) complex of N,N'-bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctane, (bme*-daco)Ni, mono- and bis-methylated thioether compounds were isolated. Both are crystallographically and electrochemically characterized and compared to analogues of N,N'-bis(2-mercaptoethyl)-1,5-diazacyclooctane, (bme-daco)Ni. Density functional theory calculations carried out at the B3LYP level using the LANL2DZ basis set with modified exponents compared HOMO/LUMO energies for the dithiolates, the mono-S-methylated and bis-S-methylated complexes. The presence of the methyl groups on the alpha-carbon next to the sulfur creates steric encumbrance about the thiolate sulfurs, but there was found no significant differences in the frontier molecular orbitals. The more positive shifts of the Ni(II/I) reduction potentials are reflected by changes in LUMO energies upon S-methylation. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00575-7
• 作为产物：
  描述：

  [1,5-bis(2-mercapto-2-methylpropane)-1,5-diazacyclooctanato]nickel(II) 在 CH₃I 作用下， 以 乙腈 为溶剂， 以86%的产率得到[1-(2-mercapto-2-methylpropyl)-5-(2-thia-3,3-dimethylbutyl)-1,5-diazacyclooctanato]nickel(II) iodide complex
  参考文献：
  名称：

  Correlation of electrochemistry, nucleophilicity and density functional calculations of the cis-dithiolate (bme*-daco)Ni

  摘要：

  Upon the sequential stoichiometric addition of methyl iodide to acetonitrile solutions of the square planar nickel (II) complex of N,N'-bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctane, (bme*-daco)Ni, mono- and bis-methylated thioether compounds were isolated. Both are crystallographically and electrochemically characterized and compared to analogues of N,N'-bis(2-mercaptoethyl)-1,5-diazacyclooctane, (bme-daco)Ni. Density functional theory calculations carried out at the B3LYP level using the LANL2DZ basis set with modified exponents compared HOMO/LUMO energies for the dithiolates, the mono-S-methylated and bis-S-methylated complexes. The presence of the methyl groups on the alpha-carbon next to the sulfur creates steric encumbrance about the thiolate sulfurs, but there was found no significant differences in the frontier molecular orbitals. The more positive shifts of the Ni(II/I) reduction potentials are reflected by changes in LUMO energies upon S-methylation. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00575-7