| 194734-47-9

• CAS: 194734-47-9
• 化学式: BF₄*C₄₂H₆₂N₃O₆Zn*H₂O
• 分子量: 875.181
• InChiKey: NQDVPSPFWAJTQI-UHFFFAOYSA-M

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：

  在 KOH 作用下， 以 甲醇 为溶剂， 以56%的产率得到
  参考文献：
  名称：

  Phenoxyl Radical Complexes of Zinc(II)

  摘要：

  A series of phenoxyl radical complexes of zinc(II) have been generated in solution and, in one instance, isolated as solid material (5) in order to study their spectroscopic features by EPR, resonance Raman, and UV-vis spectroscopy. They serve as model complexes for the active form of the copper containing fungal enzyme galactose oxidase. The complexes [Zn((LH2)-H-1)]BF4 . H2O (1), [Zn((LH2)-H-2)]BF4 . H2O (2), [Zn((LH)-H-2)] (2a), [Zn(L-3)(Ph(2)acac)] (3), [Zn(L-4)(Ph(2)acac)] (4), and [Zn(L-4)(Me-acac)] (6) were synthesized from solutions of Zn(BF4)(2) . 4H(2)O and the corresponding ligand ((LH3)-H-1=1,4,7-tris(3,5-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclonane; (LH3)-H-2=1,4,7-tris(3-tert-butyl-5-methoxy-2-hydroxybenzyl)-1,4,7-triazacyclonane; (LH)-H-3=1,4-dimethyl-7-(3,5-di-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclononane; (LH)-H-4=1,4-dimethyl-7-(3-tert-butyl-5-methoxy-2-hydroxybenzyl)-1,4,7-triazacyclononane, Ph(2)acac(-)=1,3-diphenyl-1,3-propanedionate, and Me-acac(-)=3-methyl-2,4-pentanedionate). Complexes 2, 3.0.5 toluene.1n-hexane, and 4 were structurally characterized by single-crystal X-ray crystallography. An electrochemical investigation of these complexes in CH3CN and/or CH2Cl2 solution revealed that the coordinated phenolate ligands undergo reversible one-electron oxidations with formation of coordinated phenoxyl radicals. Synthetically, the microcrystalline, paramagnetic (mu(eff)=1.7 mu(B)), solid material of [Zn(L-4)(Ph(2)acac)]PF6 (5) was produced by one electron oxidation of 4 by 1 equiv of ferrocenium hexafluorophosphate in dry CH2Cl2. Oxidation of coordinated phenol pendent arms in 1, 2, and 2a occurs at significantly higher potentials and is irreversible. Electronic (UV-vis), electron paramagnetic resonance (EPR), and resonance Raman (RR) spectra of the radicals have been studied in solution and allow the description of the electronic structure of these coordinated phenoxyl radical complexes.

  DOI：

  10.1021/ja970417d
• 作为产物：
  描述：

  zinc(II) tetrafluoroborate tetrahydrate 、 1,4,7-tris(3-tert-butyl-2-hydroxy-5-methoxybenzyl)-1,4,7-triazacyclononane 以 乙腈 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Phenoxyl Radical Complexes of Zinc(II)

  摘要：

  A series of phenoxyl radical complexes of zinc(II) have been generated in solution and, in one instance, isolated as solid material (5) in order to study their spectroscopic features by EPR, resonance Raman, and UV-vis spectroscopy. They serve as model complexes for the active form of the copper containing fungal enzyme galactose oxidase. The complexes [Zn((LH2)-H-1)]BF4 . H2O (1), [Zn((LH2)-H-2)]BF4 . H2O (2), [Zn((LH)-H-2)] (2a), [Zn(L-3)(Ph(2)acac)] (3), [Zn(L-4)(Ph(2)acac)] (4), and [Zn(L-4)(Me-acac)] (6) were synthesized from solutions of Zn(BF4)(2) . 4H(2)O and the corresponding ligand ((LH3)-H-1=1,4,7-tris(3,5-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclonane; (LH3)-H-2=1,4,7-tris(3-tert-butyl-5-methoxy-2-hydroxybenzyl)-1,4,7-triazacyclonane; (LH)-H-3=1,4-dimethyl-7-(3,5-di-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclononane; (LH)-H-4=1,4-dimethyl-7-(3-tert-butyl-5-methoxy-2-hydroxybenzyl)-1,4,7-triazacyclononane, Ph(2)acac(-)=1,3-diphenyl-1,3-propanedionate, and Me-acac(-)=3-methyl-2,4-pentanedionate). Complexes 2, 3.0.5 toluene.1n-hexane, and 4 were structurally characterized by single-crystal X-ray crystallography. An electrochemical investigation of these complexes in CH3CN and/or CH2Cl2 solution revealed that the coordinated phenolate ligands undergo reversible one-electron oxidations with formation of coordinated phenoxyl radicals. Synthetically, the microcrystalline, paramagnetic (mu(eff)=1.7 mu(B)), solid material of [Zn(L-4)(Ph(2)acac)]PF6 (5) was produced by one electron oxidation of 4 by 1 equiv of ferrocenium hexafluorophosphate in dry CH2Cl2. Oxidation of coordinated phenol pendent arms in 1, 2, and 2a occurs at significantly higher potentials and is irreversible. Electronic (UV-vis), electron paramagnetic resonance (EPR), and resonance Raman (RR) spectra of the radicals have been studied in solution and allow the description of the electronic structure of these coordinated phenoxyl radical complexes.

  DOI：

  10.1021/ja970417d