title: Synthesis and characterization of the Keggin-type ruthenium-nitrido derivative [PW11O39{RuN}]4- and evidence of its electrophilic reactivity.
abstract: The ruthenium-nitrido POM derivative [PW11O39{RuVIN}]4- has been synthesized by reaction between [PW11O39]7- and [RuVINCl5]2- or [RuVINCl4]-. Its molecular structure has been confirmed from multinuclear 31P and 183W NMR spectroscopy together with an EXAFS study, while the oxidation state of the ruthenium bearing the nitrido ligand has been inferred both from 183W NMR and XANES analysis at the Ru-K edge. The potential of [PW11O39{RuVIN}]4- in N-atom transfer reactions has been demonstrated through reaction with triphenylphosphine, which ultimately leads to the release of the bis(triphenylphosphane)iminium cation [PPh3=N=PPh3]+ through several intermediates, among which the phosphoraniminato derivative [PW11O39{RuVNPh3}]3- has been structurally characterized. Its unusual oxidation state is in accordance with its EPR spectrum.
authors.affiliation: Laboratoire de Chimie Inorganique et Matériaux Moléculaires, UMR CNRS 7071, Université Pierre et Marie Curie-Paris6, Institut de Chimie Moléculaire FR2769, 4 Place Jussieu, Case 42, 75252 Paris Cedex 05, France.
authors.forename: Vanina
authors.initials: V
authors.lastname: Lahootun
authors.forename: Claire
authors.initials: C
authors.lastname: Besson
authors.forename: Richard
authors.initials: R
authors.lastname: Villanneau
authors.forename: Françoise
authors.initials: F
authors.lastname: Villain
authors.forename: Lise-Marie
authors.initials: LM
authors.lastname: Chamoreau
authors.forename: Kamal
authors.initials: K
authors.lastname: Boubekeur
authors.forename: Sébastien
authors.initials: S
authors.lastname: Blanchard
authors.forename: René
authors.initials: R
authors.lastname: Thouvenot
authors.forename: Anna
authors.initials: A
authors.lastname: Proust