Theoretical Study of Substituent Effect in Aryl Group Migration in (para-C6H4X)Mn(CO)5 Complexes

详细

In this study, we report substituent effect on aryl group migration in (para-C₆H₄X)Mn(CO)₅ complexes using mpw1pw91 quantum chemical calculations. These calculations reveal good linear relationships between barrier energy (ΔE), activation energy (ΔH^‡), activation free energy (ΔG^‡) values and rate constants with Hammett constants of X-substituents. The occupancy values of Mn–CO_cis and Mn–C(O)-(para-C₆H₄X) bonds in reactant, transition state and product were calculated by Natural bond orbital (NBO) method.