title: Mild N-O Bond Cleavage Reactions of a Pyramidalized Nitrosyl Ligand Bridging a Dimolybdenum Center.
abstract: Complex [Mo2Cp2(μ-PCy2)(μ-NO)(NO)2] (1) was prepared by reacting [Mo2Cp2(μ-H)(μ-PCy2)(CO)4] with 2 equiv of [NO]BF4 and then treating the resulting product [Mo2Cp2(μ-PCy2)(CO)2(NO)2](BF4) with NaNO2 at 323 K, and it was shown to display a bridging nitrosyl ligand with significant pyramidalization at the N atom, a circumstance related to an unusual behavior concerning degradation of the bridging nitrosyl. Indeed, complex 1 reacts with HBF4·OEt2 to give the nitroxyl-bridged derivative [Mo2Cp2(μ-PCy2)(μ-κ(1):η(2)-HNO)(NO)2](BF4), is reduced by Zn(Hg) in the presence of trace H2O to give the amido complex [Mo2Cp2(μ-PCy2)(μ-NH2)(NO)2], and reacts with excess P(OPh)3 to give the phosphoraniminato-bridged derivative [Mo2Cp2(μ-PCy2){μ-NP(OPh)3}(NO)2].
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.affiliation: Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo , E-33071 Oviedo, Spain.
authors.forename: M Esther
authors.initials: ME
authors.lastname: García
authors.affiliation: Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo , E-33071 Oviedo, Spain.
authors.forename: Daniel
authors.initials: D
authors.lastname: García-Vivó
authors.affiliation: Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo , E-33071 Oviedo, Spain.
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Ruiz
authors.affiliation: Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo , E-33071 Oviedo, Spain.
authors.forename: Adrián
authors.initials: A
authors.lastname: Toyos