title: Mild P4 activation to give an anionic diphosphorus complex with a dual binding ability at a single P site.
abstract: The anion [Mo(2)Cp(2)(μ-PCy(2))(μ-CO)(2)](-) (1; Li(+) salt) reacts at 290 K with P(4) to give the diphosphorus-bridged complex [Mo(2)Cp(2)(μ-PCy(2))(CO)(2)(μ-κ(2):κ(2)-P(2))](-) (2). The latter reacts with MeI and ClSnPh(3) through a single P atom to give respectively diphosphenyl [Mo(2)Cp(2)(μ-PCy(2))(CO)(2)(μ-κ(2):κ(2)-P(2)Me)] (3) and stannyl [Mo(2)Cp(2)(μ-PCy(2))(CO)(2){μ-κ(2):κ(2)-P(2)(SnPh(3))}] (4) derivatives, with the P-P-Sn angle in 4 being unexpectedly acute [80.3(1)°]. According to density functional theory calculations, this novel nucleophilic behavior of 1 is derived from its anionic nature, thus enabling the P(2) ligand to act in a π-donor-like fashion.
authors.affiliation: Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, E 33071 Oviedo, Spain.
authors.forename: M Angeles
authors.initials: MA
authors.lastname: Alvarez
authors.forename: M Esther
authors.initials: ME
authors.lastname: García
authors.forename: Daniel
authors.initials: D
authors.lastname: García-Vivó
authors.forename: Alberto
authors.initials: A
authors.lastname: Ramos
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Ruiz