Abstract
The effect of chemical element on the reactivity for carbazolation reaction of phenylacetylene utilizing G13(C(6)F(5))(3) (Lewis acid) and G15-carbazole (Lewis base) was theoretically investigated using density functional theory (M06-2X-D3/def2-TZVP), where G13 represents Group 13 elements and G15 represents Group 15 elements. Through activation strain model (ASM) analysis, it is apparent that the reactivity of the entire carbazolation reaction is chiefly governed by the structural strain energy of the alkyne fragment. In other words, if G13(C(6)F(5))(3) or G15-carbazole features an atomic radius that is either too small (e.g., B atom) or too large (e.g., Tl or Bi atom), it results in inadequate orbital overlap between the reactants due to the impact of steric effects. This, in turn, results in an elevation of the activation energy for such reactions, thereby impeding the alkyne from undergoing the carbazole catalytic reaction. In light of the above analyses, our theoretical findings suggest that, except for Tl(C(6)F(5))(3), the other four Lewis acid catalysts (B(C(6)F(5))(3), Al(C(6)F(5))(3), Ga((C(6)F(5))(3), and In((C(6)F(5))(3)) demonstrate effectiveness in catalyzing the carbazolation reaction of alkyne alongside with N-carbazole. Additionally, it is anticipated that, among the five categories of G15-carbazole molecules studied, only N-carbazole can participate in the carbazolation reaction with alkyne catalyzed by B(C(6)F(5))(3), considering both kinetic and thermodynamic factors at room temperature. Our theoretical investigations, as outlined in this study, indicate that the carbazolation reaction of the alkyne, catalyzed by G13(C(6)F(5))(3) and G15-carbazole, follows Hammond's postulate. To put it more plainly, when the transition state of the chemical reaction occurs earlier, it results in a decrease in activation energy.