Quantum Chemical Characterization of Urea Methanolysis: Mechanistic Pathways and Organotin-Catalyzed DMC Formation

The methanolysis of urea represents a promising green route for the synthesis of dimethyl carbonate (DMC), a versatile compound with applications in sustainable chemistry and energy storage. In this work, a comprehensive quantum chemical investigation of the reaction mechanism is presented using density functional theory (DFT), focusing on both uncatalyzed and organotin-catalyzed systems, considering both stepwise and concerted pathways. For MC production, both the stepwise and the concerted mechanisms mediated by a methanol dimer exhibit the lowest activation enthalpies. Consequently, an effective activation enthalpy of 24.0 kcal/mol was determined, in excellent agreement with the experimental value of 23.45 kcal/mol. In contrast, the bimolecular stepwise and concerted models exhibited higher barriers (ΔH^‡ ≈ 42–52 kcal/mol). Entropy values indicated that mechanisms with two methanol molecules involve higher preorganization (ΔS^‡ ≈ −60 cal/mol K), compared to −30 cal/mol K in single-molecule pathways. For DMC production from the methyl carbamate intermediate, the rate-limiting step, it was analyzed with and without an organotin catalyst. Catalysis lowers the activation enthalpy by approximately 10 kcal/mol, yielding a value of 24.9 kcal/mol for the methanol monomer catalyzed system, in good agreement with the experimental ΔH^‡ of 24.3 kcal/mol. To deepen mechanistic understanding, we employed advanced quantum descriptors including reaction force analysis, reaction electronic flux (REF), and natural bond orbital (NBO) charge evolution. These tools revealed synchronous bond rearrangements and electronic polarization effects that govern transition state stability, mainly by the electronic charges of the carbon atom in the carbonyl group and the amine group in the sense C^δ+—N^δ-. This study provides novel mechanistic insights into the dual role of hydrogen bonding and Lewis acid catalysis in DMC synthesis and demonstrates the utility of quantum chemical tools in elucidating complex reaction pathways, offering a foundation for rational catalyst design.