阳离子稀土化合物催化氢烷氧化和氢硫化反应的研究

项目名称： 阳离子稀土化合物催化氢烷氧化和氢硫化反应的研究

项目编号： No.21272168

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 数理科学和化学

项目作者： 徐凡

作者单位： 苏州大学

项目金额： 80万元

中文摘要： 阳离子稀土化合物通常具有强于相应中性稀土化合物的Lewis酸性。利用这一特性而将阳离子稀土化合物用于催化有机反应方面的研究是一以往较少被关注的领域。另一方面，碳碳重键的氢元素化反应是符合时代需要的高度原子经济性的碳-杂键生成手段。 本项目将在已有探索工作的基础上，合成几类不同配位环境的阳离子型稀土化合物并用于催化氢烷氧化反应和氢硫化反应，系统研究它们的催化活性和选择性，了解催化剂结构对反应活性和选择性的影响规律，比较阳离子稀土化合物与相应的中性稀土化合物作用于这些反应中的机理的差异，开发用于氢烷氧化、氢硫化反应的高效、高选择性稀土催化剂，发展原子经济性生成C─O、C─S键的高活性、高选择性的方法。

中文关键词： 阳离子稀土化合物；氢烷氧化反应；氢硫化反应；催化活性；选择性

英文摘要： The Lewis acidity of cationic rare-earth metal complexes is commonly higher than that of the corresponding neutral complexes. However, application of cationic rare-earth metal complexes as Lewis acid-type catalysts in organic synthesis has been neglected for a long time. Besides, hydroelementation reactions of unsaturated C─C bonds represent an efficient and atom-economical approach for the introduction of heteroelements into carbon-based structures. Based on our previous work, some cationic rare-earth metal complexes will be synthesized and used as Lewis acid-type catalysts for hydroalkoxylation and hydrothiolation of alkene, alkyne, allene, and conjugated diene. The catalytic activities of these cationic rare-earth metal complexes will be studied and compared with those of the corresponding neutral complexes. The effect of the coordination sphere around the cationic rare-earth metal centers on their Lewis acidity will be investigated, and the differences in mechanism between the hydroelementation processes catalyzed by cationic and neutral rare-earth metal complexes will be discussed. The focus of the project is to understand the relationship between the structure of these cationic rare-earth metal complexes and the activity and selectivity of the reactions. Based on the results obtained from this research, s

英文关键词： cationic rare-earth metal complex；hydroalkoxylation；hydrothiolation；catalytic activity；selectivity