artículo
pi-donor/acceptor effect on lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands
Fecha
2007Registro en:
10.1021/jp0727594
1089-5639
MEDLINE:17595070
WOS:000247966600055
Autor
Mac Leod Carey, Desmond
Munoz Castro, Alvaro
Bustos, Carlos J.
Manriquez, Juan M.
Arratia Perez, Ramiro
Institución
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 pi-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 pi-acceptor ligands. These pi-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.