Global and local reactivity and activation patterns of HOOX (X = H, NO2, CO2-, SO3-) peroxides with solvent effects

Aparicio, F; Contreras R.; Galván M.; Cedillo, A

Abstract

A detailed analysis of the global and local reactivity patterns of neutral and charged peroxides, including hydrogen peroxide (HOOH), peroxynitric acid (HOONO2), the peroxymonocarbonic ion (HOOCO2-), and the peroxymonosulfate ion (HOOSO3-) in the presence of a polar solvent (water) is presented. The polar solvent effects are included using an isodensity surface polarized continuum model (IPCM). The (1,2) hydrogen-shift reaction for these peroxides is studied. The transition states involved in the (1,2) hydrogen shift have been located and characterized at the B3LYP/6-311G** level of theory. The global analysis shows that, although the replacement of one hydrogen atom in HOOH by a neutral NO 2 group enhances both the global softness and global electrophilicity, the substitution of one hydrogen atom by charged CO 2- and SO3- groups results in a significant electrophilic deactivation of HOOCO2- and a moderate electrophilic activation of HOOSO3-. This result is observed in both the ground state and in some activated forms involved in the (1,2) hydrogen rearrangement. The local analysis, however, shows that the transition-state structures for the same rearrangement of HOOH and the HOOCO2- ion display an electrophilicity-enhanced pattern at the oxygen atom that is being deprotonated, thereby suggesting that this activated form is more likely to be involved in the oxygen-transfer reactions. The site-activation analysis performed on the basis of the variations in local softness from the ground to the transition states is also consistent with this local reactivity picture.

Más información

Título según WOS: Global and local reactivity and activation patterns of HOOX (X = H, NO2, CO2-, SO3-) peroxides with solvent effects
Título según SCOPUS: Global and Local Reactivity and Activation Patterns of HOOX (X = H, NO 2, CO2-, SO3-) Peroxides with Solvent Effects
Título de la Revista: JOURNAL OF PHYSICAL CHEMISTRY A
Volumen: 107
Número: 47
Editorial: AMER CHEMICAL SOC
Fecha de publicación: 2003
Página de inicio: 10098
Página final: 10104
Idioma: English
URL: http://pubs.acs.org/doi/abs/10.1021/jp034936g
DOI:

10.1021/jp034936g

Notas: ISI, SCOPUS