A computational study on the insertion of CO2 into (PSiP) palladium allyl sigma-bond

作者：Wang Qin; Guo Cai Hong^*; Ren Ying; Wu Hai Shun

来源：Journal of Molecular Modeling, 2015, 21(5): 122.

DOI：10.1007/s00894-015-2678-1

• Carbon dioxide
• DFT
• ONIOM
• Palladium
• Regioselectivity

The insertion of CO2 into the (PSiP) palladium-allyl bond has been investigated using DFT. Three possible modes of CO2 insertion into (PSiP) Pd-allyl bond have been calculated, that is, direct 1.2-insertion mode, metallo-ene mode, and S(E)2 mode. The metallo-ene mode is the most favorable via the six-membered ring transition state. The results of calculations are consistent with the regioselectivity observed experimentally. The steric and electronic effects of different phosphine substituents have been evaluated by ONIOM and energy decomposition analysis (EDA) methods. For the phosphine substituents P(i-Pr)(2) and PPh2, the contribution of electronic effect is greater than that of steric effect for the CO2 insertion into (PSiP) Pd-allyl bond; while for the phosphine substituent PMe2, the contribution of steric effect is slightly greater than that of electronic effect.

• 出版日期2015-5
• 单位山西师范大学