钼、钨系过氧化物在催化Sharpless烯烃环氧化反应中的应用  

The Sharpless Epoxidation of Molybdenum Peroxide and Tungsten Peroxide

作　　者：金飞[1] 丁杭军[1] 栾奕[1] 王戈[1] 

机构地区：[1]北京科技大学材料科学与工程学院,北京100083

出　　处：《化学进展》2008年第12期1886-1895,共10页Progress in Chemistry

基　　金：国家高技术发展计划(863)项目(No.2006AA03Z459);新世纪优秀人才支持计划(No.NCZT-05-0103)资助

摘　　要：钼、钨系过氧化物是非常重要的Sharpless烯烃环氧化催化剂,有着非常广泛的工业发展前景。本文综述了钼、钨系过氧化物的种类、结构、合成方法及催化活性,分析了各种钼、钨系过氧化物的特点以及在催化环氧化领域的发展现状。同时,本文还讨论了钼、钨系过氧化物催化烯烃环氧化反应的机理。评述了在催化环氧化领域中两种主要理论——Mimoun机理与Sharpless机理的争论焦点及发展现状,以及计算化学对两种理论中间过渡态的研究进展,并且重点分析了Sharpless机理的过渡态结构。此外,本文还综述了影响钼、钨系过氧化物催化剂反应活性的各种因素以及质子所产生的副反应。最后,本文对应用于催化环氧化领域的钼、钨系过氧化物未来的研究方向提出了建议。Peroxo molybdenum and tungsten complexes are very important catalysts in the Sharpless olefin epoxidation, which are potential materials for the catalytic industrialization. The types, structures, synthesis and applications of per oxo molybdenum and tungsten complexes are reviewed in this article. The characteristics and recent development in epoxidation are also discussed. On the other hand, the epoxidation mechanism is discussed. The argument and recent development of two epoxidation theories Mimoun mechanism and Sharpless mechanism are reviewed, the recent research progress of calculated chemistry for the transition structure is discussed, and the transition structure in Sharpless mechanism is mainly discussed. The factors which may affect the catalytic activity are summarized, and the side reactions caused by proton are reviewed. Finally, suggestions for further research of epoxidation are proposed.

关 键 词：钼过氧化物 钨过氧化物 催化环氧化 Sharpless机理 

分 类 号：O614.6[理学—无机化学] O621.36[理学—化学]