Probing a General Strategy to Break the C-C Bond of Benzene by a Cyclic (Alkyl)(Amino)Aluminyl Anion.

The oxidative addition of C-C bonds in aromatic hydrocarbons by low valent main group species has attracted considerable attention from both theoretical and experimental chemists due to the big challenge in breaking their aromaticity. Herein, a general strategy to break the C-C bonds in benzene by cyclic (alkyl)(amino)aluminyl anion is demonstrated via density functional theory (DFT) calculations. The results suggest that the activation of the C-C bond of benzene by this anion is both kinetically and thermodynamically unfavorable whereas introducing electron-withdrawing groups makes such C-C bond activation becomes favorable both kinetically and thermodynamically. Such a sharp change on the kinetics and thermodynamics could be rationalized by the frontier molecular orbital theory by decreasing the lowest unoccupied molecular orbitals of the mono- and disubstituted benzenes. Aromaticity is found to stabilize the transition state for the ring open step. All these findings can help develop the chemistry of small-molecule activation.