REACTION ASPECTS OF A MU -PEROXO BINUCLEAR COPPER(II) COMPLEX
REACTION ASPECTS OF A MU -PEROXO BINUCLEAR COPPER(II) COMPLEX
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Mu-PEROXO 双核铜(II) 络合物的反应方面
DOI：
10.1021/ja00180a026
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发表时间：
1990
影响因子：
15
通讯作者：
Y. Moro
中科院分区：
文献类型：
--
作者：
N. Kitajima;Takayuki Koda;Y. Iwata;Y. Moro
研究了μ-过氧双核铜(II)配合物[Cu(Hb(3，5-Me2PZ)3)]2(O2)(1)与多种底物的反应活性。PPh3和CO不被1氧化，它们通过置换反应生成单核铜(I)配合物铜(L)(Hb(3，5-Me2Pz)3)(L=CO，PPh3)。环己烯只有在有氧条件下才被氧化成2-环己烯-1-醇等含氧产物，标记实验证实，进入产物中的氧原子来自外源氧，而不是来自μ-过氧络合物中的过氧化氢离子。苯酚和邻苯二酚在厌氧条件下发生氧化偶联，而在氧气气氛下，苯二酚的氧化偶联和氧化生成苯二酚。在动力学结果的基础上，提出了μ-Peroxo络合物中O-O键的均溶断裂与氧自由基链反应的氧化反应机理
The reactivity of a μ-peroxo binuclear copper (II) complex [Cu(HB(3,5-Me 2 pz) 3 )] 2 (O 2 ) (1) toward a variety of substrates is described. PPh 3 and CO are not oxidized by 1; they generate mononuclear copper (I) complexes Cu(L)(HB(3,5-Me 2 pz) 3 ) (L=CO, PPh 3 ) via displacement reactions. Cyclohexene is oxidized to oxygenated products such as 2-cyclohexen-1-ol only under aerobic conditions, and labeling experiments established that the oxygen atoms incorporated into the products come from the exogeneous dioxygen, not from the peroxide ion in the μ-peroxo complex. Phenols and a catechol are oxidatively coupled under anaerobic conditions, while under a dioxygen atmosphere, both oxidatively coupling and oxygenation to give benzoquinones are observed. On the basis of kinetic results, a mechanism is proposed for the oxygenation reactions in which homolytic cleavage of the O-O bond in the μ-peroxo complex is followed by free radical chain reactions with dioxygen