title: Pi-donor/acceptor effect on Lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands.
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 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.
authors.affiliation: Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Correo 22, Santiago, Chile.
authors.forename: Desmond Mac-Leod
authors.initials: DM
authors.lastname: Carey
authors.forename: Alvaro
authors.initials: A
authors.lastname: Muñoz-Castro
authors.forename: Carlos J
authors.initials: CJ
authors.lastname: Bustos
authors.forename: Juan M
authors.initials: JM
authors.lastname: Manríquez
authors.forename: Ramiro
authors.initials: R
authors.lastname: Arratia-Pérez
mesh_terms: D004563:Electrochemistry; D004735:Energy Transfer; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D008982:Molybdenum; D009584:Nitrogen; D010100:Oxygen