Selective Oxidation of Thioanisole with Hydrogen Peroxide using Copper Complexes Encapsulated in Zeolite: Formation of a Thermally Stable and Reactive Copper Hydroperoxo Species,ACS Catalysis

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Selective Oxidation of Thioanisole with Hydrogen Peroxide using Copper Complexes Encapsulated in Zeolite: Formation of a Thermally Stable and Reactive Copper Hydroperoxo Species
ACS Catalysis ( IF 11.3 ) Pub Date : 2018-02-15 00:00:00 , DOI: 10.1021/acscatal.7b04092
Syuhei Yamaguchi ₁ , Akinori Suzuki ₁ , Makoto Togawa ₁ , Maiko Nishibori ₂ , Hidenori Yahiro ₁

Affiliation

[Cu(terpy)]²⁺ complexes encapsulated into Na-Y zeolite ([Cu(terpy)]²⁺@Y) were prepared, and their catalytic activities for the oxidation of sulfides using hydrogen peroxide were investigated. Several spectroscopic results, as well as elemental analysis, demonstrated the formation of [Cu(terpy)]²⁺ complexes in supercages of Y-zeolite. [Cu(terpy)]²⁺@Y exhibited high selectivity for the oxidation of thioanisole into methylphenylsulfoxide when H₂O₂ was used. The kinetic study of this oxidation at the catalyst [Cu(terpy)]²⁺@Y suggests that the reaction of [Cu(terpy)]²⁺ species with H₂O₂ is the rate-determining step. The oxidation of thioanisole, benzene, and 2-phenylethylamine using [[Cu(terpy)]²⁺@Y]*, which was prepared from the reaction between [Cu(terpy)]²⁺@Y and H₂O₂, quantitatively proceeded to methylphenylsulfoxide, phenol, and 2-amino-1-phenylethanol, respectively. The reaction of [Cu(terpy)]²⁺@Y and H₂O₂ was found to yield thermally stable but active Cu^II-OOH species in [Cu(terpy)]²⁺@Y.

中文翻译：

使用包封在沸石中的铜络合物用过氧化氢选择性氧化硫代茴香醚：热稳定和反应性的氢过氧铜物种的形成。

制备了包裹在Na-Y沸石中的[Cu（terpy）] ²⁺配合物（[Cu（terpy）] ²⁺ @Y），并研究了它们对使用过氧化氢氧化硫化物的催化活性。几个光谱结果以及元素分析表明，在Y型沸石的超笼中形成了[Cu（terpy）] ²⁺络合物。当使用H ₂ O ₂时，[Cu（terpy）] ²⁺ @Y对硫代苯甲醚氧化为甲基苯基亚砜具有很高的选择性。在催化剂[Cu（terpy）] ²⁺ @Y上的氧化动力学研究表明，[Cu（terpy）] ²⁺物种与H ₂ O _2反应是速率确定步骤。茴香硫醚，苯，和2-苯乙胺的使用[[铜（三联吡啶）]氧化²⁺ Y] *，将其从物[Cu（三联吡啶）]之间的反应来制备²⁺ @Y和H ₂ ö ₂，定量分别制得甲基苯基亚砜，苯酚和2-氨基-1-苯基乙醇。的[铜（三联吡啶）]将反应²⁺ @Y和H ₂ ö ₂被发现产生热稳定的，但活性的Cu ^II在[铜（三联吡啶）] -OOH物种²⁺ @Y。

更新日期：2018-02-15

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