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.