Quantum-Chemical Modeling of Photochemical Reaction between Nitromethane and Olefins to Form Olefin Oxides

Resumo

The reaction between olefins and nitro compounds in the T₁ state in the gas phase has been simulated using the uB3LYP/6-311g ++(d,p) method. The reaction mechanism has been studied and the activation energies for the interaction between nitromethane and ethene, propene, butene-1, butene-2, and isobutene have been determined. It has been found that the interaction between olefins and nitromethane in the triplet state (T₁) occurs in three stages. In the first reaction, nitromethane is excited to the S₁ state followed by the intersystem crossing to the T₁ state; in the second one, nitromethane in the T₁ state interacts with the olefin to form an intermediate biradical; in the third, the product of the second reaction decomposes to form nitrosomethane and olefin oxide.