Synthesis and Characterization of the Keggin-Type Ruthenium-Nitrido Derivative [PW 11 O 39 {RuN}] 4- and Evidence of Its Electrophilic Reactivity
Résumé
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.
Domaines
ChimieOrigine | Fichiers produits par l'(les) auteur(s) |
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