科研之友
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摘要
Methanol assisted and protected proton transfers from the amide nitrogen to carbonyl oxygen atom in model peptide compound formamide have been investigated employing the B3LYP/6-311++G(d,p) level of theory. In the vicinity of formamide (F) and formamidic acid (FA), three different regions are considered to form hydrogen bond with methanol. Methanol molecule only in one of them can assist the proton transfer reaction while in other two sites can protect formamide from tautomerization. Totally, 27 geometries, including nine important transition states, were optimized, and their geometric parameters have also been discussed in detail. The thermodynamic and kinetic parameters, such as tautomeric energies, equilibrium constants, barrier heights, and rate constants have been predicted, respectively. In addition, the factors influencing the thermodynamic and kinetic parameters, such as temperature dependences, and solvent effects have also been explored qualitatively. Computational results show that the lowest proton transfer barrier heights are 83.30 (61.61) kJ/mol without (with) ZPVE correction for the assistance of two methanol molecules, which are also lower than that of the water-assisted process. Nonspecific solvent effects have also been taken into account by using the IPCM model of methanol. The tautomerization energies and the barrier heights are increased for these proton transfer systems because of the bulk solvent, which imply that the tautomerization of F becomes less favorable in the polar medium.
