标题：Theoretical investigation on the isomerization reaction of 4-phenyl-hexa-1,5-enyne catalyzed by homogeneous Au catalysts
作者：Liu, Y.;Zhang, D.;Bi, S.
作者机构：[Liu, Y] Key Lab of Colloid and Interface Chemistry, Shandong University, Ministry of Education, Jinan, 250100, China;[ Zhang, D] Key Lab of Colloid a 更多
通讯作者地址：[Zhang, DJ]Shandong Univ, Inst Theoret Chem, Minist Educ, Key Lab Colloid & Interface Chem, Jinan 250100, Peoples R China.
来源：The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory
摘要：By carrying out density functional theory calculations, we have performed a detailed mechanism study for the cycloisomerization reaction of 4-phenyl-hexa-1,5-enyne catalyzed by homogeneous gold to better understand the observed different catalytic activity of several catalysts, including (PPh _3)AuBF_4, (PPh_3)AuCl, AuCl_3, and AuCl. In all situations, the reaction is found to involve two major steps: the initial nucleophilic addition of the alkynyl onto the alkene group and the subsequent 1,2-H migration. It is found that the potential energy surface profiles of systems are very different when different catalysts are used. For (PMe_3)AuBF_4- and (PMe_3)AuCl-mediated systems, the nucleophilic addition is the rate-determining step, and the calculated free energy barriers are 15.2 and 41.9 kcal/mol, respectively. In contrast, for AuCl_3- and AuCl-mediated systems, the reactions are controlled by the dissociations of catalysts from the product-like intermediates, and the calculated dissociation energies are 18.1 and 21.7 kcal/mol, respectively, which are larger than both the corresponding free energy barriers of the nucleophilic addition and the H-migration processes (8.5 and 7.3 kcal/mol for the AuCl _3-mediated reaction, and 16.9 and 11.3 kcal/mol for the AuCl-mediated reaction). These results can rationalize the early experimental observations that the reactant conversion rates are 100, 0, and 50% when using (PPh _3)AuBF_4, (PPh_3)AuCl, and AuCl_3 as catalysts, respectively. The present study indicates that both the ligand and counterion of homogeneous Au catalysts importantly influence their catalytic activities, whereas the oxidation state of Au is not a crucial factor controlling the reactivity.