Mechanistic Insights into the Reactivity and Activation Barrier Origins for CO2 Capture by Heavy Group-14 Imine Analogues.

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Using M06-2X-D3/def2-TZVP, the [2 + 2] cycloaddition reactions of carbon dioxide with the heavy imine analogues G14=N-Rea (G14 = Group 14 element) were investigated. The theoretical evidence reveals that the nature of the doubly bonded G14=N moiety in heavy imine analogues, G14=N-Rea (L1L2G14=N-L3), is characterized by the electron-sharing interaction between triplet L1L2G14 and triplet N-L3 fragments. Based on our theoretical studies, except for the carbon-based imine, all four heavy imine analogues with Si=N, Ge=N, Sn=N, and Pb=N groups can easily engage in [2 + 2] cycloaddition reactions with CO2. Energy decomposition analysis-natural orbitals for chemical valence analyses and the FMO theory strongly suggest that in the CO2 capture reaction by heavy imine analogues G14=N-Rea, the primary bonding interaction is the occupied p-π orbital (G14=N-Rea) → vacant p-π* orbital (CO2) interaction, instead of the empty p-π* orbital (G14=N-Rea) ← filled p-π orbital (CO2) interaction. The activation barrier of the CO2 capture reactions by G14=N-Rea molecules is primarily determined by the deformation energy of CO2. Shaik's valence bond state correlation diagram model, used to rationalize the computed results, indicates that the singlet-triplet energy splitting of G14=N-Rea is a key factor in determining the reaction barrier for the current CO2 capture reactions.