pi-donor/acceptor effect on lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands

Carey, DML; Munoz-Castro, A; Bustos, CJ; Manriquez, JM; Arratia-Perez, R

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. © 2007 American Chemical Society.

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Título según WOS: pi-donor/acceptor effect on lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands
Título según SCOPUS: p-Donor/acceptor effect on Lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands
Título de la Revista: JOURNAL OF PHYSICAL CHEMISTRY A
Volumen: 111
Número: 28
Editorial: AMER CHEMICAL SOC
Fecha de publicación: 2007
Página de inicio: 6563
Página final: 6567
Idioma: English
URL: http://pubs.acs.org/doi/abs/10.1021/jp0727594
DOI:

10.1021/jp0727594

Notas: ISI, SCOPUS