Global and local reactivity descriptors based on quadratic and linear energy models for alpha,beta-unsaturated organic compounds

Javier Oller, Patricia Pérez, Paul W. Ayers, Esteban Vöhringer-Martinez

Resultado de la investigación: Article

2 Citas (Scopus)

Resumen

Global and local descriptors of chemical reactivity can be derived from conceptual density functional theory. Their explicit form, however, depends on how the energy is defined as a function of the number of electrons. Within the existing interpolation models, here, the quadratic and the linear energy model were used to derive global descriptors as the electrophilicity and nucleophilicity (defined as the negative of the ionization potential) and local descriptors employing either the corresponding condensed Fukui function in the linear model or the local response of the global descriptor in the quadratic model. The ability of these descriptors to predict the reactivity of molecules with more than one reactive site was first studied on a set of α, β-unsaturated ketones, where experimental rate constants for the nucleophilic attack is known. With the validated descriptors the reactivity of α, β-unsaturated carboxylic compounds with different heteroatoms as α, β-unsaturated thioesters, esters, and amides was addressed as alternative substrates for enzymatic CO2 fixation. Carbon dioxide fixation involves the reduction of the neutral α, β-unsaturated carboxylic compounds by a nucleophilic attack of a hydride anion from NADPH and the following electrophilic attack by carbon dioxide. It was found that condensed values of the linear Fukui function within the fragment of molecular response approximation describe best the reactivity of α, β-unsaturated ketones. For the two relevant processes involved in CO2 fixation the amides present the largest reactivity in vacuum and in aqueous solution compared to the esters and thioesters and may, therefore, serve as alternative substrates of carboxylases.

Idioma originalEnglish
Número de artículoe25706
PublicaciónInternational Journal of Quantum Chemistry
Volumen118
N.º20
DOI
EstadoPublished - 15 oct 2018

Huella dactilar

organic compounds
Organic compounds
reactivity
attack
Ketones
Carbon Dioxide
Amides
Esters
ketones
amides
carbon dioxide
esters
Chemical reactivity
energy
Ionization potential
Substrates
NADP
Hydrides
Density functional theory
Anions

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Citar esto

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abstract = "Global and local descriptors of chemical reactivity can be derived from conceptual density functional theory. Their explicit form, however, depends on how the energy is defined as a function of the number of electrons. Within the existing interpolation models, here, the quadratic and the linear energy model were used to derive global descriptors as the electrophilicity and nucleophilicity (defined as the negative of the ionization potential) and local descriptors employing either the corresponding condensed Fukui function in the linear model or the local response of the global descriptor in the quadratic model. The ability of these descriptors to predict the reactivity of molecules with more than one reactive site was first studied on a set of α, β-unsaturated ketones, where experimental rate constants for the nucleophilic attack is known. With the validated descriptors the reactivity of α, β-unsaturated carboxylic compounds with different heteroatoms as α, β-unsaturated thioesters, esters, and amides was addressed as alternative substrates for enzymatic CO2 fixation. Carbon dioxide fixation involves the reduction of the neutral α, β-unsaturated carboxylic compounds by a nucleophilic attack of a hydride anion from NADPH and the following electrophilic attack by carbon dioxide. It was found that condensed values of the linear Fukui function within the fragment of molecular response approximation describe best the reactivity of α, β-unsaturated ketones. For the two relevant processes involved in CO2 fixation the amides present the largest reactivity in vacuum and in aqueous solution compared to the esters and thioesters and may, therefore, serve as alternative substrates of carboxylases.",
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Global and local reactivity descriptors based on quadratic and linear energy models for alpha,beta-unsaturated organic compounds. / Oller, Javier; Pérez, Patricia; Ayers, Paul W.; Vöhringer-Martinez, Esteban.

En: International Journal of Quantum Chemistry, Vol. 118, N.º 20, e25706, 15.10.2018.

Resultado de la investigación: Article

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AU - Ayers, Paul W.

AU - Vöhringer-Martinez, Esteban

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AB - Global and local descriptors of chemical reactivity can be derived from conceptual density functional theory. Their explicit form, however, depends on how the energy is defined as a function of the number of electrons. Within the existing interpolation models, here, the quadratic and the linear energy model were used to derive global descriptors as the electrophilicity and nucleophilicity (defined as the negative of the ionization potential) and local descriptors employing either the corresponding condensed Fukui function in the linear model or the local response of the global descriptor in the quadratic model. The ability of these descriptors to predict the reactivity of molecules with more than one reactive site was first studied on a set of α, β-unsaturated ketones, where experimental rate constants for the nucleophilic attack is known. With the validated descriptors the reactivity of α, β-unsaturated carboxylic compounds with different heteroatoms as α, β-unsaturated thioesters, esters, and amides was addressed as alternative substrates for enzymatic CO2 fixation. Carbon dioxide fixation involves the reduction of the neutral α, β-unsaturated carboxylic compounds by a nucleophilic attack of a hydride anion from NADPH and the following electrophilic attack by carbon dioxide. It was found that condensed values of the linear Fukui function within the fragment of molecular response approximation describe best the reactivity of α, β-unsaturated ketones. For the two relevant processes involved in CO2 fixation the amides present the largest reactivity in vacuum and in aqueous solution compared to the esters and thioesters and may, therefore, serve as alternative substrates of carboxylases.

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