物理化学学报2011，Vol.27Issue(9)：2043-2050,8.
AuClx (x=1,3)催化2-炔丙基苯酮与苯炔环化反应机理
AuClx (x=1, 3)-Catalyzed Benzannulation Mechanisms between 2-Propynyl-hypnone and Benzyne
摘要
Abstract
The AuClx (x=1,3)-catalyzed benzannulation mechanisms between benzyne and 2-propynylhypnone were investigated using B3LYP,B3PW91,UB3LYP,and the second-order Mφller-Plesset perturbation (MP2) methods with the LanL2DZ basis set for Au and the 6-31G*,6-311 ++G** basis sets for C,H,O,Cl.For the AuCl or AuCl3 catalysts the reaction occurs through both the [4 + 2] and the [3 + 2]benzannulation pathways to yield the product.With AuCl,the reaction occurs mainly through the [4 + 2]reaction pathway because of this pathway's low activation free energy.With AuCl3,the reaction occurs by the [4 + 2] and the [3 + 2] reaction pathways.These two pathways are competitive because of their close activation free energies.An analysis of these results indicates that the gold oxidation states change the reaction mechanisms and greatly influence the reaction barriers.The calculated results indicate that the AuCl catalyst is more effective than AuCl3 because in the reaction catalyzed by AuCl the activation free energy of the rate determining step is 11.18 kJ· mol-1 lower than that of the reaction catalyzed by AuCl3.These results are in good agreement with the experimental observations.关键词
金催化剂/密度泛函理论/反应机理/[4+2]环化途径/[3+2]环化途径Key words
Gold catalyst/Density functional theory/Reaction mechanism/[4+2] Benzannulation/[3+2] Benzannulation分类
化学化工引用本文复制引用
朱元强,郭建春,叶仲斌..AuClx (x=1,3)催化2-炔丙基苯酮与苯炔环化反应机理[J].物理化学学报,2011,27(9):2043-2050,8.基金项目
四川省教育厅科研项目(09ZB099)资助 The project was supported by the Scientific Research Fund of Sichuan Provincial Education Department,China (09ZB099). （09ZB099）
