Theoretical study of intramolecular proton transfer reactions in some thiooxalic acid derivatives

Eduardo Chamorro, Alejandro Toro-Labbe, Patricio Fuentealba

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

17 Citas (Scopus)

Resumen

The intramolecular proton-transfer reactions in some thiooxalic acid derivatives HY - C(=O)-C(=S)-XH, (1) X=O, Y=O; (2) X=O, Y=S; (3) X=S, Y=S, have been studied in the gas-phase at the B3LYP/6-311+G(d,p) level of theory. Reactions are shown to proceed via a two step mechanism more than through single concerted interconversions. Four-membered transition states are involved along the oxygen to oxygen, sulfur to oxygen, and sulfur to sulfur, single proton-transfer processes. The double proton-transfer reaction in these systems is a competitive and coupled process with the conformational rearrangement through the central C-C bond. Reaction mechanisms have been discussed in terms of global and local chemical reactivity descriptors. The electronic nature of the transferred hydrogen has been explicitly examined using the topological analysis of the electron localization function (ELF). Ion-pair like transition structures with charge separations of 0.48e, 0.42e, and 0.18e have been found for the oxygen to oxygen, sulfur to oxygen, and sulfur to sulfur proton-transfer reactions, respectively, in these type of proton-transfer processes.

Idioma originalInglés
Páginas (desde-hasta)3891-3898
Número de páginas8
PublicaciónJournal of Physical Chemistry A
Volumen106
N.º15
DOI
EstadoPublicada - 18 abr 2002

Áreas temáticas de ASJC Scopus

  • Química física y teórica

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