Synthesis, characterization and dioxygen reactivity of copper(i) complexes with glycoligands
作者:Ziad Damaj、Federico Cisnetti、Laurent Dupont、Eric Henon、Clotilde Policar、Emmanuel Guillon
DOI:10.1039/b801109e
日期:——
A new family of copper(I) complexes with “glycoligands” containing a central saccharide scaffold, with 2-picolyl ether groups or 2-picolylamine or N-imidazolylamine groups, has been prepared and characterized. For this purpose, the following tetradentate ligands have been synthesized: methyl 2,3-di-O-(2-picolyl)-α-D-lyxofuranoside (L1), 1,5-anhydro-2-deoxy-3,4-di-O-(2-picolyl)-D-galactitol (L2), 5-(amino-N-(2-salicyl))-5-deoxy-1,2-O-isopropylidene-3-O-(2-picolyl)-α-D-xylofuranose (L3), and 5-(amino-N-(2-salicyl))-5-deoxy-1,2-O-isopropylidene-3-O-(methylimidazol-2-yl)-α-D-xylofuranose (L4). The ligands and the complexes were characterized by elemental analysis, IR, 1H and 13C NMR spectroscopies, ESI mass spectrometry, and cyclic voltammetry. Collaterally with the experimental work, HF-DFT(B3LYP/6–31G*) computations were performed to obtain additional structural information. The Cu(I) complexes are found to be pentacoordinated. The redox properties and the O2-reactivity of the CuILn complexes have been studied. Reactions of Cu(I) complexes with dioxygen in ethanol yield stable Cu(II) complexes as confirmed by UV-visible spectrophotometry and EPR spectroscopy.
一个新的铜(I)络合物与“糖配体”包含一个中心糖支架,具有2-吡啶甲基醚基团或2-吡啶甲基胺或N-咪唑胺基团,已被制备和表征。为此,合成了以下四齿配体:甲基 2,3-二-O-(2-吡啶甲基)-α-D-lyxofuranoside (L1), 1,5-anHydro-2-deoxy-3,4-二-O-(2-吡啶甲基)-D-半乳糖醇 (L2), 5-(氨基-N-(2-水杨基))-5-脱氧-1,2-O-异亚丙基-3-O-(2-吡啶甲基)-α-D-呋喃木糖(L3)和 5-(氨基-N-(2-水杨基))-5-脱氧-1,2-O-异亚丙基-3-O-(甲基咪唑-2-基) -α-D-呋喃木糖 (L4)。通过元素分析、IR、1H 和 13C NMR 光谱、ESI 质谱和循环伏安法对配体和配合物进行了表征。在实验工作的同时,还进行了 HF-DFT(B3LYP/6–31G*) 计算以获得额外的结构信息。发现 Cu(I) 配合物是五配位的。研究了 CuILn 配合物的氧化还原性质和 O2 反应性。 Cu(I) 络合物与乙醇中的分子氧反应产生稳定的 Cu(II) 络合物,经紫外-可见分光光度法和 EPR 光谱法证实。