In Silico Investigation of Ligand-Regulated Palladium-Catalyzed Formic Acid Dehydrative Decomposition under Acidic Conditions

In silico investigation of ligand-regulated palladium-catalyzed formic acid dehydrative decomposition to carbon monoxide under acidic conditions was conducted. The pyridyl group implanted in the pytbpx ligand is found to mainly contribute to enhancing the activity of the palladium catalyst. para-Toluenesulfonic acid (PTSA) displays a specific role for regenerating active species and suppressing dehydrogenation during HCOOH dehydration, especially when the bis-protonated Pd-pytbpx complex is formed with excessive PTSA loading. However, the Pd-dtbpx system is too complicated to elucidate the HCOOH decomposition route only by one kind of species. According to the mechanism hereby supposed, introducing electron-donating substitution at the para position of pyridyl rings may further improve the dehydration activity of Pd-pytbpx.