π-Donor/acceptor effect on Lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands

Desmond Mac Leod Carey, Alvaro Muñoz-Castro, Carlos J. Bustos, Juan M. Manríquez, Ramiro Arratia-Pérez

Resultado de la investigación: Article

15 Citas (Scopus)

Resumen

The electronic structures of Lindqvist type functionalized polyoxometalates (POM) ([Mo6O18R]n-- R = O, NO, NAr, NNAr, NNAr2; n = 2, 3) have been investigated using density functional methods. We discuss the role of the replacement of terminal oxo ligands by π-donor/acceptor multiple-bonded nitrogenous ligands on the basis of geometrical parameters, charge analyses, reactivity indexes, and vibrational spectra. The calculated reactivity indexes (chemical potential, electronegativity, hardness, and electrophilicity) indicate that the most reactive functionalized POMs are those substituted by π-acceptor ligands. These π-acceptor ligands induce a decrease in the hardness and an increase in the chemical potential and electrophilicity, thus increasing the reactivity. Our calculations are in reasonable agreement with reported experimental data.

Idioma originalEnglish
Páginas (desde-hasta)6563-6567
Número de páginas5
PublicaciónJournal of Physical Chemistry A
Volumen111
N.º28
DOI
EstadoPublished - 19 jul 2007

Huella dactilar

Ligands
ligands
reactivity
Chemical potential
hardness
Hardness
Electronegativity
Vibrational spectra
vibrational spectra
Electronic structure
electronic structure

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Citar esto

Carey, Desmond Mac Leod ; Muñoz-Castro, Alvaro ; Bustos, Carlos J. ; Manríquez, Juan M. ; Arratia-Pérez, Ramiro. / π-Donor/acceptor effect on Lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands. En: Journal of Physical Chemistry A. 2007 ; Vol. 111, N.º 28. pp. 6563-6567.
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abstract = "The electronic structures of Lindqvist type functionalized polyoxometalates (POM) ([Mo6O18R]n-- R = O, NO, NAr, NNAr, NNAr2; n = 2, 3) have been investigated using density functional methods. We discuss the role of the replacement of terminal oxo ligands by π-donor/acceptor multiple-bonded nitrogenous ligands on the basis of geometrical parameters, charge analyses, reactivity indexes, and vibrational spectra. The calculated reactivity indexes (chemical potential, electronegativity, hardness, and electrophilicity) indicate that the most reactive functionalized POMs are those substituted by π-acceptor ligands. These π-acceptor ligands induce a decrease in the hardness and an increase in the chemical potential and electrophilicity, thus increasing the reactivity. Our calculations are in reasonable agreement with reported experimental data.",
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π-Donor/acceptor effect on Lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands. / Carey, Desmond Mac Leod; Muñoz-Castro, Alvaro; Bustos, Carlos J.; Manríquez, Juan M.; Arratia-Pérez, Ramiro.

En: Journal of Physical Chemistry A, Vol. 111, N.º 28, 19.07.2007, p. 6563-6567.

Resultado de la investigación: Article

TY - JOUR

T1 - π-Donor/acceptor effect on Lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands

AU - Carey, Desmond Mac Leod

AU - Muñoz-Castro, Alvaro

AU - Bustos, Carlos J.

AU - Manríquez, Juan M.

AU - Arratia-Pérez, Ramiro

PY - 2007/7/19

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N2 - The electronic structures of Lindqvist type functionalized polyoxometalates (POM) ([Mo6O18R]n-- R = O, NO, NAr, NNAr, NNAr2; n = 2, 3) have been investigated using density functional methods. We discuss the role of the replacement of terminal oxo ligands by π-donor/acceptor multiple-bonded nitrogenous ligands on the basis of geometrical parameters, charge analyses, reactivity indexes, and vibrational spectra. The calculated reactivity indexes (chemical potential, electronegativity, hardness, and electrophilicity) indicate that the most reactive functionalized POMs are those substituted by π-acceptor ligands. These π-acceptor ligands induce a decrease in the hardness and an increase in the chemical potential and electrophilicity, thus increasing the reactivity. Our calculations are in reasonable agreement with reported experimental data.

AB - The electronic structures of Lindqvist type functionalized polyoxometalates (POM) ([Mo6O18R]n-- R = O, NO, NAr, NNAr, NNAr2; n = 2, 3) have been investigated using density functional methods. We discuss the role of the replacement of terminal oxo ligands by π-donor/acceptor multiple-bonded nitrogenous ligands on the basis of geometrical parameters, charge analyses, reactivity indexes, and vibrational spectra. The calculated reactivity indexes (chemical potential, electronegativity, hardness, and electrophilicity) indicate that the most reactive functionalized POMs are those substituted by π-acceptor ligands. These π-acceptor ligands induce a decrease in the hardness and an increase in the chemical potential and electrophilicity, thus increasing the reactivity. Our calculations are in reasonable agreement with reported experimental data.

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