均相催化氧化中的活性中间体多样性  

Diversity of Active Intermediates in Homogeneous Catalytic Oxidations

作　　者：汪玉娟[1] 徐杰[2] 尹国川[1] 

机构地区：[1]华中科技大学化学与化工学院,武汉430074 [2]中国科学院大连化学物理研究所,大连116023

出　　处：《化学进展》2012年第2期203-211,共9页Progress in Chemistry

基　　金：国家自然科学基金项目(No.20973069)资助

摘　　要：过渡金属离子在各种化学及生物氧化中扮演着极为重要的作用,现有的研究表明参与催化氧化的关键活性物种已不再局限于金属氧物种(Mn+O),金属氢氧物种(Mn+—OH)与金属过氧物种(Mn+—OOH)均被发现能够参与各种氧化反应。有些有机化合物也能直接催化有机物的氧化反应,同时,相似的有机物如NADH和辅酶Q一直在生物代谢中发挥着重要作用。但是,现有的研究结果还难以清楚解释生物体系中各种氧化酶在不同的氧化反应中选择特定活性物种的内在原因。因此,了解这些活性物种之间的氧化性能异同性将非常有助于了解酶对它们的选择,进而理解酶的催化氧化机理,为药物设计提供理论基础,同时也有助于设计新的氧化催化剂。本文对在各种均相催化氧化及生物氧化反应中出现的主要活性中间体种类、各中间体的反应性能、反应机理进行了总结,并就现有的实验数据对过渡金属氧物种与氢氧物种的氧化性能相似性及相异性进行了初步评述。Transition metal ions play significant roles in versatile biological and chemical oxidations. In addition to the generally believed metal oxo functional groups （ Mn2＋- 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 hydroxofunctional groups have also been briefly discussed.

关 键 词：催化氧化 活性中间体 反应活性异同性 

分 类 号：O643.3[理学—物理化学] Q554.1[理学—化学]