Nickel/zinc-catalyzed decarbonylative addition of anhydrides to alkynes: A DFT study

作者：Meng, Qingxi; Li, Ming^*

来源：Journal of Molecular Modeling, 2013, 19(10): 4545-4554.

DOI：10.1007/s00894-013-1968-8

• Alkynes
• Anhydrides
• Nickel catalyst
• Decarbonylative addition
• DFT
• Reaction mechanism
• ZnCl2

Density functional theory (DFT) was used to investigate the nickel- or nickel(0)/zinc- catalyzed decarbonylative addition of phthalic anhydrides to alkynes. All intermediates and transition states were optimized completely at the B3LYP/6-31+G(d,p) level. Calculated results indicated that the decarbonylative addition of phthalic anhydrides to alkynes was exergonic, and the total free energy released was -87.6 kJ mol(-1). In the five-coordinated complexes M4a and M4b, the insertion reaction of alkynes into the Ni-C bond occurred prior to that into the Ni-O bond. The nickel(0)/zinc-catalyzed decarbonylative addition was much more dominant than the nickel-catalyzed one in whole catalytic decarbonylative addition. The reaction channel CA -> M1'-> T1'-> M2'-> T2'-> M3a'-> M4a'-> T3a1'-> M5a1' -> T4a1'-> M6a'-> P was the most favorable among all reaction pathways of the nickel- or nickel(0)/zinc- catalyzed decarbonylative addition of phthalic anhydrides to alkynes. And the alkyne insertion reaction was the rate-determining step for this channel. The additive ZnCl2 had a significant effect, and it might change greatly the electron and geometry structures of those intermediates and transition states. On the whole, the solvent effect decreased the free energy barriers.

• 出版日期2013-10
• 单位山东农业大学; 西南大学