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. Here, we demonstrate a general strategy to break the C-C bonds in benzene by cyclic (alkyl)(amino)aluminyl anion via density functional theory (DFT) calculations. Our 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.

https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202203216