Acetylene cyclotrimerization catalyzed by PdCl2 and CuCl2 in the gas phase: A theoretical study

作者：Deng, Zhe-Peng; Wang, Yong-Cheng^*; Zhe, Jian-Wu; Sun, Yu; Liu, Guang-Ming; Ma, Pan-Pan; Niu, Gui-Ping; Jin, Neng-Zhi; Sheng, Yang; Da, Hu

来源：Computational and Theoretical Chemistry, 2017, 1104: 18-23.

DOI：10.1016/j.comptc.2017.01.027

• DFT
• Palladium chloride
• Acetylene
• Cyclotrimerization
• Benzene
• FMO

With high activity of IL electron system, acetylene can produce cyclic trimerization (Cyclotrimerization) under certain conditions to generate benzene. The reaction mechanism for acetylene cyclotrimerization catalyzed by PdCl2 together with CuCl2 has been investigated using the density functional theory (DM calculations at the B3LYP/6-31+G(d,p) level. The computational results suggested that one acetylene molecule combined with metal center of PdCl2 to yield intermediate 1M1, and then the second acetylene molecule participates into react with metal center of PdCl2 which leads to intermediate IM2. The intermediate IM2 continued to react with the third acetylene molecule to get the final product benzene via three possible paths (I, II and III). According to the energy profiles, path III is the most favorable one with lower energy barrier and is kinetically available. The addition of copper chloride plays an important role in improving the reaction rate and regioselectivity and reducing the possibility of dimerization and polymerization reactions. The results could provide valuable insights into these types of interactions and related ones.

• 出版日期2017-3-15
• 单位甘肃省计算中心; 西北民族大学; 西北师范大学