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• Review •

Diversity of Active Intermediates in Homogeneous Catalytic Oxidations

Wang Yujuan1, Xu Jie2, Yin Guochuan1*   

  1. 1. School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China;
    2. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
  • Received: Revised: Online: Published:
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Transition metal ions play significant roles in versatile biological and chemical oxidations. In addition to the generally believed metal oxo functional groups(Mn+ O), the metal hydroxo (Mn+-OH)and hydroperoxide functional groups (Mn+-OOH) have also been proposed to serve as the key active intermediates in versatile oxidation processes. However, the reasons why natural redox metalloenzymes make use of a metal oxo or hydroxo group to serve as their active intermediates in specific cases are not fully understood. In addition, certain organic compounds such as benzoquinone and organic N-oxide have also been reported to serve as catalyst in many chemical oxidation reactions, meanwhile, similar organic compounds like NADH and Coenzyme Q have been long believed to play the key roles in versatile biological metabolisms. Apparently, clarifying the oxidative relationships of these active intermediates would help to understand the enzymes' selections on them, thus promote understanding of their mechanisms and help the rational design of medicines, also it would benefit the design of selective oxidation catalysts. Herein, these active intermediates occurring in biological and chemical oxidation events are summarized in this paper. Their oxidative properties and related mechanisms have been discussed in text. Meanwhile, based on the available publications, the oxidative similarities and differences of the metal oxo with its corresponding hydroxo functional groups have also been briefly discussed. Contents
1 Introduction
2 Traditional theories in catalytic oxidations
3 New discoveries for the active metal intermediates in oxidations
4 The redox active organic intermediates in oxidations
5 The reactivity relationships of the metal oxo and its corresponding hydroxo moieties
6 Perspective
Key words: catalytic oxidation, active intermediates, reactivity similarities and differences

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