Understanding the Highly Varying pKa of Arylamines. A Perspective from the Average Local Ionization Condensed-to-Atom Framework

Resultado de la investigación: Article

5 Citas (Scopus)

Resumen

The highly varying experimental pKa values for 36 arylamines spanning 7 orders of magnitude is carefully examined. Within this framework, a valence condensed-to-atom model for the average ionization energy is introduced and tested. The theoretical approach is connected to orbital Fukui functions directly mapped into semilocal or regional site-specific responses. It is revealed that the average local ionization energies associated with the amino nitrogen atom is linearly correlated to the basicity of the substituted arylamines, properly reproducing the experimental ordering of basicity. The condensed-to-atom descriptor exhibits a high predictive power, providing a new direct reactivity evaluation of significant value. (Graph Presented)

Idioma originalEnglish
Páginas (desde-hasta)8156-8162
Número de páginas7
PublicaciónJournal of Physical Chemistry A
Volumen119
N.º29
DOI
EstadoPublished - 23 jul 2015

Huella dactilar

Ionization
Ionization potential
Alkalinity
ionization
Atoms
nitrogen atoms
atoms
reactivity
valence
orbitals
energy
evaluation
Nitrogen

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Citar esto

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abstract = "The highly varying experimental pKa values for 36 arylamines spanning 7 orders of magnitude is carefully examined. Within this framework, a valence condensed-to-atom model for the average ionization energy is introduced and tested. The theoretical approach is connected to orbital Fukui functions directly mapped into semilocal or regional site-specific responses. It is revealed that the average local ionization energies associated with the amino nitrogen atom is linearly correlated to the basicity of the substituted arylamines, properly reproducing the experimental ordering of basicity. The condensed-to-atom descriptor exhibits a high predictive power, providing a new direct reactivity evaluation of significant value. (Graph Presented)",
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AU - Chamorro, Eduardo

AU - Duque-Noreña, Mario

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Y1 - 2015/7/23

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AB - The highly varying experimental pKa values for 36 arylamines spanning 7 orders of magnitude is carefully examined. Within this framework, a valence condensed-to-atom model for the average ionization energy is introduced and tested. The theoretical approach is connected to orbital Fukui functions directly mapped into semilocal or regional site-specific responses. It is revealed that the average local ionization energies associated with the amino nitrogen atom is linearly correlated to the basicity of the substituted arylamines, properly reproducing the experimental ordering of basicity. The condensed-to-atom descriptor exhibits a high predictive power, providing a new direct reactivity evaluation of significant value. (Graph Presented)

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JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

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