The Bimolecular Catalytic Transformation of Methyl Vinyl Ketone Oxide: A DFT Study

Abstract The bimolecular reactions of methyl vinyl ketone oxide (MVK-OO) with H2O, H2S, NH3, their dimer forms, and CH3NH2, have been studied. The reactions of (H2O)2 and (NH3)2 exhibit an effect of reducing the free energies of activation (ΔG‡); a catalytic behavior. The former energy barriers decrease by 20 kJ mol-1 while the latter by 14 kJ mol-1. In contrast, additional molecules in H2S reactions increase the calculated ΔG‡ values by 22 kJ mol-1. The calculations of MVK-OO + CH3NH2 predict ΔG‡ = 26 kJ mol-1, lower than the catalyzed reactions of H2O, H2S, and NH3. Additional molecules in CH3NH2 reactions lead to negligible effects on the energy, except for the (CH3NH2…H2O) reaction, where ΔG‡ is reduced by 10 kJ mol-1. The formation of a carbonyl hydroperoxide (via MVK-OO + HCO2H) is predicted to be the least favorable pathway with ΔG‡ values in the range of 61 to 69 kJ mol-1.