Assisted and Protected Effects of Methanol Molecules on Intramolecular Proton Transfer in Formamide Studied with the Density Functional Theory

Du, M.; Qin, M.; Fu, A.; Zhou, Z.

Artykuł - szczegóły

Tytuł artykułu

Assisted and Protected Effects of Methanol Molecules on Intramolecular Proton Transfer in Formamide Studied with the Density Functional Theory

Autorzy

Du M. , Qin M. , Fu A. , Zhou Z.

Identyfikatory

Warianty tytułu

Języki publikacji

Abstrakty

Methanol assisted and protected proton transfers from the amide nitrogen to carbonyl oxygen atom inmodel 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.

Słowa kluczowe

proton transfer barrier heights solvent effects thermodynamic and kinetic parameters

Wydawca

Polskie Towarzystwo Chemiczne

Czasopismo

Polish Journal of Chemistry

Rocznik

2007

Tom

Vol. 81, nr 3

Strony

369--380

Opis fizyczny

Bibliogr. 36 poz., , rys.

Twórcy

autor

Du M.

autor

Qin M.

autor

Fu A.

autor

Zhou Z.

Department of Chemistry, Qufu Normal University, Shandong, Qufu, 273165, P.R. China

Bibliografia

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Typ dokumentu

Bibliografia

Identyfikator YADDA

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