Effect of Mono- and Di-hydration on the Intramolecular Proton Transfers and Stability of Cyanuric Acid Isomers: A DFT Study
Structural and thermodynamic properties of 10 isomers of cyanuric acid were studied in aqueous and gas phases, employing B3LYP/6-311++G(d,p) method. The aromaticities of these isomers were evaluated using nucleus-independent chemical shift (NICS) index. The calculations showed that as the number of the ketogroups increases the stability of the isomers increases and the aromaticity decreases. Mono- and di-hydrations of the isomers did not change the stability trend, so that the tri-keto isomer was the most stable isomer amongthe hydrated and non-hydrated isomers. The activation energies (Ea) of the intramolecular proton transfers (tautomerisms) and energy barriers of H-rotations around its C-O axis in enolic isomers were calculated. The energy barriers were smaller than 45 kJ/mol for the H-rotations while the Ea values of the proton transfers were in the range of 130-210 kJ/mol. Effect of micro-hydrations on the transition state structures and the energy barriers of the tautomerisms were investigated. The mono- and di-hydrations lower the activation energies to100-130 kJ/mol and 110-145 kJ/mol, respectively.
Volume 134, 2022
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