Synthesis and Characterization of the Keggin-Type Ruthenium-Nitrido Derivative [PW 11 O 39 {RuN}] 4- and Evidence of Its Electrophilic Reactivity

Vanina Lahootun (1) , Claire Besson (2) , Richard Villanneau (3, 4) , Françoise Villain (2) , Lise-Marie Chamoreau (5) , Kamal Boubekeur (1) , Sébastien Blanchard (3) , René Thouvenot (1) , Anna Proust (1)

1 CIM2 - Laboratoire de Chimie Inorganique et Matériaux Moléculaires
2 CIM2 - Laboratoire de Chimie Inorganique et Matériaux Moléculaires
3 IPCM - Institut Parisien de Chimie Moléculaire
4 E-POM - Edifices PolyMétalliques
5 IPCM - Institut Parisien de Chimie Moléculaire

The ruthenium-nitrido 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 spectroscopies together with an EXAFS study, while the oxidation state of the ruthenium bearing the nitrido ligand has been inferred from an XANES analysis at the Ru-K edge. The potentialities of [PW11O39{RuVIN}]4- in N-atom transfer reactions has been evidenced through the 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.

Mots clés: Anions; Cations; Oxidation state; Reaction products; Vinyl

Domaines: Chimie

Vanina Lahootun, Claire Besson, Richard Villanneau, Françoise Villain, Lise-Marie Chamoreau, et al.. Synthesis and Characterization of the Keggin-Type Ruthenium-Nitrido Derivative [PW 11 O 39 {RuN}] 4- and Evidence of Its Electrophilic Reactivity. Journal of the American Chemical Society, 2007, 129 (22), pp.7127-7135. ⟨10.1021/ja071137t⟩. ⟨hal-04564861⟩