Density-functional study on the equilibria in the ThDP activation

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

Resultado de la investigación: Article

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

Huella dactilar

Ionization
Chemical activation
activation
ionization
Thermodynamics
Equilibrium constants
Cyclohexane
thermodynamics
cycles
Density functional theory
tautomers
cyclohexane
Atoms
polarity
Geometry
Water
Substrates
density functional theory
geometry
water

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications
  • Computational Theory and Mathematics
  • Catalysis
  • Organic Chemistry
  • Inorganic Chemistry

Citar esto

Delgado, Eduardo J. ; Alderete, Joel B. ; Jaña, Gonzalo A. / Density-functional study on the equilibria in the ThDP activation. En: Journal of Molecular Modeling. 2011 ; Vol. 17, N.º 11. pp. 2735-2739.
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Density-functional study on the equilibria in the ThDP activation. / Delgado, Eduardo J.; Alderete, Joel B.; Jaña, Gonzalo A.

En: Journal of Molecular Modeling, Vol. 17, N.º 11, 11.2011, p. 2735-2739.

Resultado de la investigación: Article

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AU - Alderete, Joel B.

AU - Jaña, Gonzalo A.

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AB - 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.]

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