Density-functional study on the equilibria in the ThDP activation

Eduardo J. Delgado, Joel B. Alderete, Gonzalo A. Jaña

Resultado de la investigación: Contribución a una revistaArtículo

4 Citas (Scopus)

Resumen

The equilibria among the various ionization and tautomeric states involved in the activation of ThDP is addressed using high level density functional theory calculations, X3LYP/6-311++G(d,p)//X3LYP(PB)/6-31++G(d,p). This study provides the first theoretically derived thermodynamic data for the internal equilibria in the activation of ThDP. The role of the medium polarity on the geometry and thermodynamics of the diverse equilibria of ThDP is addressed. The media chosen are cyclohexane and water, as paradigms of apolar and polar media. The results suggest that all ionization and tautomeric states are accessible during the catalytic cycle, even in the absence of substrate, being APH + the form required to interconvert the AP and IP tautomers; and the generation of the ylide proceeds via the formation of the IP form. Additionally, the calculated ΔG° values allow to calculate all the equilibrium constants, including the pK C2 for the thiazolium C2 atom whose ionization is believed to initiate the catalytic cycle. [Figure not available: see fulltext.]

Idioma originalInglés
Páginas (desde-hasta)2735-2739
Número de páginas5
PublicaciónJournal of Molecular Modeling
Volumen17
N.º11
DOI
EstadoPublicada - nov 2011

Áreas temáticas de ASJC Scopus

  • Química física y teórica
  • Informática aplicada
  • Teoría computacional y matemáticas
  • Catálisis
  • Química orgánica
  • Química inorgánica

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