[Rh(s,s-chiraphos)]^+催化MAC氢化反应中间态的量子化学计算  

Quantum Chemistry Calculation of Intermediates of the Methyl - α - acetamidocinnamate Hydrogenation Catalyzed by Cationic [Rh(s,s-chiraphos)]^+ Complexes

作　　者：李西平[1] 陈秀敏[1] 刘有德[2] 

机构地区：[1]昆明理工大学理学院,云南昆明650093 [2]云南师范大学,云南昆明650092

出　　处：《昆明理工大学学报（理工版）》2004年第1期149-154,共6页Journal of Kunming University of Science and Technology(Natural Science Edition)

基　　金：云南省自然科学基金(项目编号:B002M);云南省教育厅科学研究基金资助(项目编号:O111058)

摘　　要：采用量子化学的ab initio方法,对膦铑络合物[Rh(s,s—chiraphos)]+催化甲基-α-乙酰氨基肉桂酸氢化反应的三个中间态的结构进行了优化,其中第一个中间态有同类中间态的x-射线衍射实验数据对照,结构数据符合较好,几个中间态的优化结果均符合此类反应的立体走向特征.说明用量子化学方法实现该类反应中间态结构的优化是方便可行的,优化结果及进一步的计算将会为反应机理研究奠定基础并提供重要信息.A theoretical study on the three cationic [Rh(s,s - chiraphos)]^+ complexes is presented which are important intermediates in the asymmetric hydrogenation affording methyl - a - acetamidocinnamate. The geometry optimizations are performed at the ab initio level, and the geometry optimized result of the first intermediate conforms perfectly to the result of x - ray diffraction experiment, and the geometry optimized results of the intermediates accord with the three - dimensional structure characters of this kind of reactions. The calculation indicates that quantum chemistry method can be used in optimizing the intermediates of this kind of reactions, and the optimized result will lay a foundation and provide important information for the reaction mechanism study.

关 键 词：[Rh(s s-chiraphos)]^+络合物 催化氢化 ab initio方法 中间态 量子化学 

分 类 号：O641.4[理学—物理化学] O641.121[理学—化学]