Theoretical modeling of the oxidation of hydrazine by iron(II) phthalocyanine in the gas phase. influence of the metal character

Gloria I. Cárdenas-Jirón, Verónica Paredes-García, Diego Venegas-Yazigi, José H. Zagal, Maritza Páez, Juan Costamagna

Resultado de la investigación: Article

13 Citas (Scopus)

Resumen

The hydrazine oxidation by iron(II) phthalocyanine (Fe(II)Pc) has been studied using an energy profile framework through quantum chemistry theoretical models calculated in the gas phase at the density functional theory B3LYP/LACVP(d) level. We applied two models of charge-transfer mechanisms previously reported (J. Phys. Chem. A 2005, 109, 1196) for the hydrazine oxidation mediated by Co(II)Pc. Model 1 consists of an alternated loss of one electron and one proton, involving anionic and neutral species. Model 2 considers an alternated loss of two electrons and two protons and includes anionic, neutral, and cationic species. Both applied models describe how the charge-transfer process occurs. In contrast with the obtained results for Co(II)Pc, we found that the hydrazine oxidation mediated by Fe(II)Pc is a fully through-bond charge-transfer mechanism. On the other hand, the use of different charge-transfer descriptors (spin density, electronic population, condensed Fukui function) showed a major contribution of the iron atom in comparison with the cobalt atom in the above-mentioned process. These results could explain the higher catalytic activity observed experimentally for Fe(II)Pc in comparison with Co(II)Pc. The applied theoretical models are a good starting point to rationalize the charge-transfer process of hydrazine oxidation mediated by Fe(II)Pc.

Idioma originalEnglish
Páginas (desde-hasta)11870-11875
Número de páginas6
PublicaciónJournal of Physical Chemistry A
Volumen110
N.º42
DOI
EstadoPublished - 26 oct 2006

Huella dactilar

hydrazine
hydrazines
Iron
Gases
Metals
Charge transfer
vapor phases
iron
Oxidation
charge transfer
oxidation
metals
Protons
Quantum chemistry
Atoms
protons
Electrons
quantum chemistry
Cobalt
Density functional theory

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Cárdenas-Jirón, Gloria I. ; Paredes-García, Verónica ; Venegas-Yazigi, Diego ; Zagal, José H. ; Páez, Maritza ; Costamagna, Juan. / Theoretical modeling of the oxidation of hydrazine by iron(II) phthalocyanine in the gas phase. influence of the metal character. En: Journal of Physical Chemistry A. 2006 ; Vol. 110, N.º 42. pp. 11870-11875.
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abstract = "The hydrazine oxidation by iron(II) phthalocyanine (Fe(II)Pc) has been studied using an energy profile framework through quantum chemistry theoretical models calculated in the gas phase at the density functional theory B3LYP/LACVP(d) level. We applied two models of charge-transfer mechanisms previously reported (J. Phys. Chem. A 2005, 109, 1196) for the hydrazine oxidation mediated by Co(II)Pc. Model 1 consists of an alternated loss of one electron and one proton, involving anionic and neutral species. Model 2 considers an alternated loss of two electrons and two protons and includes anionic, neutral, and cationic species. Both applied models describe how the charge-transfer process occurs. In contrast with the obtained results for Co(II)Pc, we found that the hydrazine oxidation mediated by Fe(II)Pc is a fully through-bond charge-transfer mechanism. On the other hand, the use of different charge-transfer descriptors (spin density, electronic population, condensed Fukui function) showed a major contribution of the iron atom in comparison with the cobalt atom in the above-mentioned process. These results could explain the higher catalytic activity observed experimentally for Fe(II)Pc in comparison with Co(II)Pc. The applied theoretical models are a good starting point to rationalize the charge-transfer process of hydrazine oxidation mediated by Fe(II)Pc.",
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Theoretical modeling of the oxidation of hydrazine by iron(II) phthalocyanine in the gas phase. influence of the metal character. / Cárdenas-Jirón, Gloria I.; Paredes-García, Verónica; Venegas-Yazigi, Diego; Zagal, José H.; Páez, Maritza; Costamagna, Juan.

En: Journal of Physical Chemistry A, Vol. 110, N.º 42, 26.10.2006, p. 11870-11875.

Resultado de la investigación: Article

TY - JOUR

T1 - Theoretical modeling of the oxidation of hydrazine by iron(II) phthalocyanine in the gas phase. influence of the metal character

AU - Cárdenas-Jirón, Gloria I.

AU - Paredes-García, Verónica

AU - Venegas-Yazigi, Diego

AU - Zagal, José H.

AU - Páez, Maritza

AU - Costamagna, Juan

PY - 2006/10/26

Y1 - 2006/10/26

N2 - The hydrazine oxidation by iron(II) phthalocyanine (Fe(II)Pc) has been studied using an energy profile framework through quantum chemistry theoretical models calculated in the gas phase at the density functional theory B3LYP/LACVP(d) level. We applied two models of charge-transfer mechanisms previously reported (J. Phys. Chem. A 2005, 109, 1196) for the hydrazine oxidation mediated by Co(II)Pc. Model 1 consists of an alternated loss of one electron and one proton, involving anionic and neutral species. Model 2 considers an alternated loss of two electrons and two protons and includes anionic, neutral, and cationic species. Both applied models describe how the charge-transfer process occurs. In contrast with the obtained results for Co(II)Pc, we found that the hydrazine oxidation mediated by Fe(II)Pc is a fully through-bond charge-transfer mechanism. On the other hand, the use of different charge-transfer descriptors (spin density, electronic population, condensed Fukui function) showed a major contribution of the iron atom in comparison with the cobalt atom in the above-mentioned process. These results could explain the higher catalytic activity observed experimentally for Fe(II)Pc in comparison with Co(II)Pc. The applied theoretical models are a good starting point to rationalize the charge-transfer process of hydrazine oxidation mediated by Fe(II)Pc.

AB - The hydrazine oxidation by iron(II) phthalocyanine (Fe(II)Pc) has been studied using an energy profile framework through quantum chemistry theoretical models calculated in the gas phase at the density functional theory B3LYP/LACVP(d) level. We applied two models of charge-transfer mechanisms previously reported (J. Phys. Chem. A 2005, 109, 1196) for the hydrazine oxidation mediated by Co(II)Pc. Model 1 consists of an alternated loss of one electron and one proton, involving anionic and neutral species. Model 2 considers an alternated loss of two electrons and two protons and includes anionic, neutral, and cationic species. Both applied models describe how the charge-transfer process occurs. In contrast with the obtained results for Co(II)Pc, we found that the hydrazine oxidation mediated by Fe(II)Pc is a fully through-bond charge-transfer mechanism. On the other hand, the use of different charge-transfer descriptors (spin density, electronic population, condensed Fukui function) showed a major contribution of the iron atom in comparison with the cobalt atom in the above-mentioned process. These results could explain the higher catalytic activity observed experimentally for Fe(II)Pc in comparison with Co(II)Pc. The applied theoretical models are a good starting point to rationalize the charge-transfer process of hydrazine oxidation mediated by Fe(II)Pc.

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