A theoretical analysis of the gas-phase protonation of hydroxylamine, methyl-derivatives and aliphatic amino acids

Patricia Pérez, Renato Contreras

Resultado de la investigación: Article

40 Citas (Scopus)

Resumen

Hydroxylamines and aliphatic amino acids present two active sites towards electrophilic attack by a proton, namely, the amino nitrogen and hydroxylic oxygen atoms. Site reactivity may be described in terms of local descriptors of chemical reactivity defined in the context of the density functional theory formulation of Parr, Pearson and Yang (DFT-PPY). We report a DFT-PPY analysis of site reactivity in hydroxylamine, methyl-derivatives of hydroxylamine and the aliphatic amino acids glycine, alanine and valine, using a simple formulation of the regional or condensed-to-atom k (fk -) Fukui function. A satisfactory qualitative correlation between this local descriptor of site reactivity and the experimental proton affinities is found. The nitrogen center appears as the preferential site of protonation. Enhancement of the site basicity at the nitrogens may be probed by variations of the Fukui function ΔfN -, with reference to the ammonia molecule; the correlation between proton affinity and the Fukui function difference is closely related to a local hard and soft acids and bases principle.

Idioma originalEnglish
Páginas (desde-hasta)239-244
Número de páginas6
PublicaciónChemical Physics Letters
Volumen293
N.º3-4
EstadoPublished - 28 ago 1998

Huella dactilar

Hydroxylamine
Protonation
amino acids
Protons
Nitrogen
reactivity
Gases
vapor phases
Derivatives
Amino Acids
Density functional theory
Hydroxylamines
formulations
nitrogen
protons
affinity
Atoms
Chemical reactivity
Valine
Alkalinity

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics
  • Physics and Astronomy(all)

Citar esto

@article{84e6c3c596404dd2a210f80447b2705f,
title = "A theoretical analysis of the gas-phase protonation of hydroxylamine, methyl-derivatives and aliphatic amino acids",
abstract = "Hydroxylamines and aliphatic amino acids present two active sites towards electrophilic attack by a proton, namely, the amino nitrogen and hydroxylic oxygen atoms. Site reactivity may be described in terms of local descriptors of chemical reactivity defined in the context of the density functional theory formulation of Parr, Pearson and Yang (DFT-PPY). We report a DFT-PPY analysis of site reactivity in hydroxylamine, methyl-derivatives of hydroxylamine and the aliphatic amino acids glycine, alanine and valine, using a simple formulation of the regional or condensed-to-atom k (fk -) Fukui function. A satisfactory qualitative correlation between this local descriptor of site reactivity and the experimental proton affinities is found. The nitrogen center appears as the preferential site of protonation. Enhancement of the site basicity at the nitrogens may be probed by variations of the Fukui function ΔfN -, with reference to the ammonia molecule; the correlation between proton affinity and the Fukui function difference is closely related to a local hard and soft acids and bases principle.",
author = "Patricia P{\'e}rez and Renato Contreras",
year = "1998",
month = "8",
day = "28",
language = "English",
volume = "293",
pages = "239--244",
journal = "Chemical Physics Letters",
issn = "0009-2614",
publisher = "Elsevier",
number = "3-4",

}

A theoretical analysis of the gas-phase protonation of hydroxylamine, methyl-derivatives and aliphatic amino acids. / Pérez, Patricia; Contreras, Renato.

En: Chemical Physics Letters, Vol. 293, N.º 3-4, 28.08.1998, p. 239-244.

Resultado de la investigación: Article

TY - JOUR

T1 - A theoretical analysis of the gas-phase protonation of hydroxylamine, methyl-derivatives and aliphatic amino acids

AU - Pérez, Patricia

AU - Contreras, Renato

PY - 1998/8/28

Y1 - 1998/8/28

N2 - Hydroxylamines and aliphatic amino acids present two active sites towards electrophilic attack by a proton, namely, the amino nitrogen and hydroxylic oxygen atoms. Site reactivity may be described in terms of local descriptors of chemical reactivity defined in the context of the density functional theory formulation of Parr, Pearson and Yang (DFT-PPY). We report a DFT-PPY analysis of site reactivity in hydroxylamine, methyl-derivatives of hydroxylamine and the aliphatic amino acids glycine, alanine and valine, using a simple formulation of the regional or condensed-to-atom k (fk -) Fukui function. A satisfactory qualitative correlation between this local descriptor of site reactivity and the experimental proton affinities is found. The nitrogen center appears as the preferential site of protonation. Enhancement of the site basicity at the nitrogens may be probed by variations of the Fukui function ΔfN -, with reference to the ammonia molecule; the correlation between proton affinity and the Fukui function difference is closely related to a local hard and soft acids and bases principle.

AB - Hydroxylamines and aliphatic amino acids present two active sites towards electrophilic attack by a proton, namely, the amino nitrogen and hydroxylic oxygen atoms. Site reactivity may be described in terms of local descriptors of chemical reactivity defined in the context of the density functional theory formulation of Parr, Pearson and Yang (DFT-PPY). We report a DFT-PPY analysis of site reactivity in hydroxylamine, methyl-derivatives of hydroxylamine and the aliphatic amino acids glycine, alanine and valine, using a simple formulation of the regional or condensed-to-atom k (fk -) Fukui function. A satisfactory qualitative correlation between this local descriptor of site reactivity and the experimental proton affinities is found. The nitrogen center appears as the preferential site of protonation. Enhancement of the site basicity at the nitrogens may be probed by variations of the Fukui function ΔfN -, with reference to the ammonia molecule; the correlation between proton affinity and the Fukui function difference is closely related to a local hard and soft acids and bases principle.

UR - http://www.scopus.com/inward/record.url?scp=0039986505&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0039986505

VL - 293

SP - 239

EP - 244

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

IS - 3-4

ER -