Unraveling the Reaction Mechanism of AlCl3-Lewis Acid Catalyzed Acylation Reaction of Pyrene from the Perspective of the Molecular Electron Density Theory

The reaction mechanism of AlCl3-Lewis acid catalyzed acylation of pyrene with methylacylium ion has been carried out at the B97X-D/6-311G(d,p) level within the Molecular Electron Density Theory (MEDT). Before to complete this work, CDFT (Conceptual DFT) analysis allows to classify both reactants as nucleophile (pyrene) and super electrophile (methylacylium ion), respectively, permitting this acylation to take place with a polar character. This polar character has been supported by high value of Global Electron Density Transfer (GEDT) recorded for each transition state. Concerning the bond changes, BET analysis reveals that a series of four Structural Stability Domains (SSDs) are required to describe the formation of new C-C and H-Cl single bonds. For the formation of C-C single bond due to the attack of methylacylium ion on pyrene, the first two stages correspond to 1) the creation of a pseudoradical center on both C carbon atoms (appearance of V(C) basin) of each reactant and 2) the creation new C-C single bond via the merger of these two previous V(C) basins. Finally, formation of H-Cl molecule occurs via cleavage of H-C bond (splitting of V(H,C) basin) and formation of new H-Cl single bond (appearance of new V(H,Cl) disynaptic basin), and the last step illustrates the regain of aromaticity of the ring engaged in the acylation reaction.

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