[Fe(1,4,7,10,13-pentaazacyclopentadecane)Cl](PF6) | 202199-30-2

• 英文名称: [Fe(1,4,7,10,13-pentaazacyclopentadecane)Cl](PF6)
• CAS: 202199-30-2
• 化学式: C₁₀H₂₅N₅*Cl*F₆P*Fe
• 分子量: 451.606
• InChiKey: GELZMZGQSUUOGK-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  ammonium hexafluorophosphate 、 1,4,7,10,13-五氮杂环十五烷 、 iron(II) chloride 以 甲醇 为溶剂， 以82%的产率得到[Fe(1,4,7,10,13-pentaazacyclopentadecane)Cl](PF6)
  参考文献：
  名称：

  Iron(III) Complexes as Superoxide Dismutase Mimics:  Synthesis, Characterization, Crystal Structure, and Superoxide Dismutase (SOD) Activity of Iron(III) Complexes Containing Pentaaza Macrocyclic Ligands

  摘要：

  Iron(III) complexes with four pentaaza macrocylic ligands, [Fe(L)Cl-2](PF6), have been synthesized, where the ligand L is 1,4,7,10,13-pentaazacyclopentadecane (L-1), 2R,3R,8S,9S-dicyclohexano-1,4,7,10,13-pentaazacyclopentadecane L-2), 2R,3R,8R,9R-dicyclohexano-1,4,7,10,13-pentaazacyclopentadecane (L-3), or 2S,5R,8S,11R,14S-pentamethyl-1,4,7,10,13-pentaazacyclopentadecane (L-4), respectively. Conductivity measurements in acetonitrile are consistent with two chloro anions coordinated to iron(III). In acetonitrile solution, all four iron complexes exhibit a reversible or quasi-reversible redox couple in the experimental range -1.5 to +1.5 V vs EAg/Ag+, and the redox potentials for those four complexes are similar (from -0.15 to -0.19 V vs NHE). In aqueous solutions, the electrochemical properties of those complexes are different from these in acetonitrile solution; the redox peaks shift more than 0.5 V more positive. The complexes with L-1, L-2, and L-3 display a reversible redox at 0.35, 0.45, and 0.43 V vs NHE, respectively, while [Fe(L-4)Cl-2](PF6) shows a cathodic peak at 0.44 V and two anodic peaks at 0.31 and 0.14 V vs NHE, respectively. The base titration results reveal that two water molecules are coordinated to the iron(III) in these complexes, pK(a1) and pK(a2): 3.46(7) and 7.31(7) for [Fe(L-1)Cl-2](PF6); 3.7(1) and 7.50(2) for [Fe(L-2)Cl-2](PF6); 4.1(1) and 7.73(2) for [Fe(L-3)Cl-2](PF6); 3.6(7) and 7.4(2) for [Fe(L-4)Cl-2](PF6). The superoxide dismutase (SOD) activity, assessed by stopped-flow experiments, reveals that all four metal complexes catalyze the fast disproportionation of superoxide in aqueous solution: at pH = 7.8, the catalyic rate constants for the complexes were 0.81 x 10(7), 1.42 x 10(7), 1.41 x 10(7), and 0.29 x 10(7) M-1 s(-1) for [Fe(L-1)Cl-2](PF6), [Fe(L-2)Cl-2](PF6), [Fe(L-3)Cl-2](PF6), and [Fe(L-4)Cl-2](PF6), respectively. The crystal structure of [Fe(L-2)Cl-2](PF6) was determined. Crystal data: triclinic, ; a = 7.367(2), b = 10.707(2), c = 17.632(2) Angstrom; alpha = 81.27(2), beta = 79.74(2), gamma = 83.38(2)degrees; R = 0.0465 for observed data (I > 2 sigma(I)). The iron is seven-coordinate with five nitrogen atoms from the pentaaza macrocylic ligand and trans-chloro anions in a pentagonal bipyramidal arrangement. The average bond lengths for Fe-N and Fe-Cl are 2.271 and 2.339 Angstrom, respectively.

  DOI：

  10.1021/ic970861h