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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Oxygen binding and activation by the complexes of PY2- and TPA-appended diphenylglycoluril receptors with copper and other metals
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Oxygen binding and activation by the complexes of PY2- and TPA-appended diphenylglycoluril receptors with copper and other metals

机译：通过PY2-和TPA附加的二苯基甘氨酰脲受体与铜和其他金属的配合物进行氧结合和活化

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摘要

The copper(I) complexes of diphenylglycoluril basket receptors 1 and 2,appended with bis(2-ethylpyridine)amine (PY2) and tris(2-methylpyridine)amine (TPA),respectively,and their dioxygen adducts were studied with low-temperature UV-vis and X-ray absorption spectroscopy (XAS).The copper(I) complex of 1,[1 centre dot Cu(I)_2] or 1a,forms a mu-eta~2:eta~2 dioxygen complex,whereas the copper(I) complex of 2,[2 centre dot Cu(I)_2] or 2a,does not form a well defined dioxygen complex,but is oxidized to Cu(II).Dioxygen is bound irreversibly to 1a and the formed complex is stable over time.The coordination geometries of the above complexes were determined by XAS,which revealed that pyridyl groups and amine N-donors participate in the coordination to Cu(I) ions in the complexes of both receptors.The catalytic activities of various metal complexes of 1 and 2,that were designed as mimics of dinuclear copper enzymes that can activate dioxygen,were investigated.Phenolic substrates that were expected to undergo aromatic hydroxylation,showed oxidative polymerization without insertion of oxygen.The mechanism of this polymerization turns out to be a radical coupling reaction as was established by experiments with the model substrate 2,4-di-tert-butylphenol.In addition to Cu(II),the Mn(III) complex of 1 and the Fe(II) complex of 2 were tested as oxidation catalysts.Oxidation of catechol was observed for the Cu(II) complex of receptor 1 but the other metal complexes did not lead to oxidation.
机译：分别研究了二苯基乙二醇尿篮篮子受体1和2的铜（I）配合物分别与双（2-乙基吡啶）胺（PY2）和三（2-甲基吡啶）胺（TPA）以及它们的双氧加合物紫外可见光谱和X射线吸收光谱（XAS）。1，[1中心点Cu（I）_2]或1a的铜（I）配合物形成mu-eta〜2：eta〜2双氧配合物，而2，[2个中心点Cu（I）_2]或2a的铜（I）络合物没有形成明确的双氧络合物，但被氧化为Cu（II）。双氧不可逆地与1a和形成的络合物结合XAS测定了上述配合物的配位几何结构，表明吡啶基和胺N供体参与了两种受体配合物对Cu（I）离子的配位作用。研究了1和2的复合物，这些复合物被设计为可激活双氧的双核铜酶的模拟物。进行芳族羟基化反应，表明没有插入氧就可以进行氧化聚合反应。这种聚合反应的机理是自由基偶联反应，这是通过模型底物2,4-二叔丁基苯酚的实验确定的。 II），测试1的Mn（III）配合物和2的Fe（II）配合物作为氧化催化剂。观察到邻苯二酚被受体1的Cu（II）配合物氧化，但其他金属配合物未导致氧化。

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