The mechanisms of C-H bond insertion and alkene cycloaddition were investigated theoretically using five model systems: group 13 analogues of the four-membered nucleophilic N-heterocyclic carbenes (NHCs) (1E; E = group 13 element). The theoretical findings indicate that, except for 1B with H2C=CH2, these four-membered NHCs undergo insertion and [1 + 2] cycloaddition reactions with difficulty because their activation barriers are quite high (31 kcal/mol). The theoretically confirmed chemical inertness of the four-membered NHCs 1Ga and 1In might explain why they have been experimentally detected at room temperature. Additionally, our theoretical observations indicate that the reactivity of these four-membered NHCs featuring a central group 13 element follows the order 1B ≫ 1Al > 1Ga > 1In > 1Tl. The theoretical examination suggests that the smaller the atomic radius of the central group 13 element in the four-membered NHC analogue is, the larger the aromaticity of this carbenic molecule is, the higher the basicity of this carbenic molecule in nature is, the larger its nucleophilic attack on other oncoming molecules is, the smaller the barrier heights of its C-H bond insertion and [1 + 2] cycloaddition reactions will be, the higher its exothermicities for these products will be, and thus, the greater its reactivity will be. Moreover, the present theoretical findings reveal that the reactivity of 1B is governed by its highest occupied molecular orbital, a nonbonding sp2 lone pair orbital. In contrast, the reactivity of the four heavier 1E' (E' = Al, Ga, In, and Tl) molecules is mainly determined by their lowest unoccupied molecular orbital, a vacant p-π orbital. The conclusions gained from this study allow many predictions to be made.
© 2021 The Authors. Published by American Chemical Society.