title: The doubly-bonded ditungsten anion [W2Cp2(μ-PPh2)(NO)2](-): an entry to the chemistry of unsaturated nitrosyl complexes.
abstract: Complex [W2Cp2(μ-I)(μ-PPh2)(NO)2] was prepared by reacting [W2Cp2(μ-I)(μ-PPh2)(CO)2] with NO at 233 K followed by decarbonylation in refluxing toluene. It was reduced by Na(Hg) in acetonitrile to give Na[W2Cp2(μ-PPh2)(NO)2], the first anionic nitrosyl complex featuring a metal-metal double bond (computed W-W = 2.580 Å). Reactions of the latter anion with (NH4)PF6 and [AuCl{P(p-tol)3}] gave the hydride [W2Cp2(μ-H)(μ-PPh2)(NO)2] and the cluster [AuW2Cp2(μ-PPh2)(NO)2{P(p-tol)3}] respectively, also featuring multiple W-W bonding (experimental W-W ca. 2.75 Å), and its reaction with S8 yielded the electron-precise derivative Na[W2Cp2(μ-PPh2)(μ-S)(NO)2], which was methylated by Me2SO4 to give the thiolate complex [W2Cp2(μ-PPh2)(μ-SMe)(NO)2].
authors.affiliation: Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, E-33071 Oviedo, Spain. mara@uniovi.es.
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: Miguel A
authors.initials: MA
authors.lastname: Ruiz
authors.forename: Adrián
authors.initials: A
authors.lastname: Toyos