Syntheses and characterization of copper complexes with the ligand 2-aminoethyl(2-pyridylmethyl)-1,2-ethanediamine (apme)

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• 作者：Diana Utz ; S ; ra Kisslinger ; Frank Hampel ; Siegfried Schindler
• 关键词：Copper(I)/(II) complexes ; Tripodal tetradentate ligands ; Dioxygen ; Crystal structures ; Copper enzymes
• 刊名：Journal of Inorganic Biochemistry
• 出版年：2008
• 期刊代码：53_01620134
• 类别：ch
• 出版时间：May 2008
• 卷：102
• 期：5-6
• 页码：1236-1245
• 文件大小：421 K

摘要

Copper(I)/(II) complexes with the ligand 2-aminoethyl(2-pyridylmethyl)1,2-ethanediamine (apme, abbreviated as PDT in the literature as well) were prepared and characterized. Crystal structures of the copper(I) complexes, [Cu₂(apme)₂]X₂ (1, 2; X = ClO₄, CF₃SO₃), showed that they are dinuclear, in contrast to the trigonal bipyramidal copper(II) complexes [Cu(apme)Cl]BPh₄ (3) and [Cu(apme)(DMF)](BPh₄)₂ (4). 1 and 2 could be investigated in solution by NMR spectroscopy and 3 and 4 by cyclovoltammetry. From the results of these studies it is clear that in solution equilibria between the dinuclear complexes 1/2 and another species exist, most likely the monomeric [Cu(apme)CH₃CN]⁺. Time-resolved UV/vis spectra at low temperatures allowed the spectroscopic detection of dioxygen adduct complexes as reactive intermediates during the oxidation of 1/2 with dioxygen that seem to play an important role in copper enzymes such as peptidylglycine-alt="greek small letter alpha" title="greek small letter alpha" border="0">-hydroxylating monooxygenase (PHM).