Activation of Carbonyl group by a Manganese Catalyst: An energy decomposition analysis

Catalysts have attracted great interest and are highly regarded in chemical synthesis and drug discovery. Transition metals complexes are receiving increasing attention worldwide as powerful homogeneous catalysts, especially for potential applications in catalysis. These complexes are powerful homogeneous catalysts for the synthesis of organic compounds using various atom donors. 1–3In this study, the reaction between ortho-quinone (o-QM) and 4-aminopyridine in the presence and in the absence of Manganese Complex (Mncatal) at the B3LYP/SVP level of theory using the Gaussian 09 program4 was investigated. Also in order to understand the nature of interactions in these compounds, the energy decomposition analysis5 (EDA) based on the ETS-NOCV, at the M06-2X/TZ2P-(ZORA)//M06-2X/def2-TZVPP level of theory has been used. In the catalyzed reaction, the catalytic activity effect of Mncatal on the interaction between o-QM and 4-aminopyridine that yields the final product was investigated. In the presence of the nanocatalyst, in addition to the formation of the Mn–O bond between o-QM and the catalyst in [Mcatal…o-QM], there is also an O…H bond between them. The values of Gibbs free energies show that this process is energetically favorable. The activation energy for Mn-catalyzed reaction is endothermic in comparison with uncatalyzed reaction. The EDA calculations showed that the ΔEels and ΔEorb terms are responsible to increase the stabilization of the Mcatal…complexes.

Keywords:

Manganese Catalyst , Density Functional Theory , Energy Decomposition Analysis