关键词: AuCl₃, 密度泛函理论, 反应机理, 炔酮内环化反应

Abstract: Density functional theory with B3LYP functionals was used to study generating phenanthrene derivatives mechanism of acetylenic-keton intramolecular cyclization reaction catalyzed by AuCl₃. It shows that the reaction can occur through [2+2] and [2+6] reaction pathways with and without AuCl₃ catalyst. Without catalyst, energy barrier of rate determining step of [2+2] pathway is lower than that of [2+6] pathway by 32.01 kJ·mol^-1. Reaction mainly occurs through [2+2] pathway. With AuCl₃ catalyst, dominent reaction pathway is still [2+2] pathway with an energy barrier of rate determining step of 137.05 kJ·mol^-1. Energy barrier of rate determining step of four-membered ring pathway with AuCl₃ catalyst is 102.72 kJ·mol^-1 lower than that of reaction without catalyst. This difference indicates that AuCl₃ is an efficient catalyst which can raise reaction rate and moderate reaction condition.

Key words: AuCl₃, density functional theory, reaction mechanism, acetylenic-keton intramolecular cyclization reaction