Nitrogen-Atom Transfer from [PW 11 O 39 Ru VI N] 4− to PPh 3

Claire Besson (1, 2) , Yurii Geletii (3) , Françoise Villain (4) , Richard Villanneau (2, 5) , Craig Hill (3) , Anna Proust (4, 2, 5)

1 CIM2 - Laboratoire de Chimie Inorganique et Matériaux Moléculaires
2 E-POM - Edifices PolyMétalliques
3 Department of Chemistry [Emory]
4 CIM2 - Laboratoire de Chimie Inorganique et Matériaux Moléculaires
5 IPCM - Institut Parisien de Chimie Moléculaire

The nitrido derivative (n Bu4N)4[PW11O39RuVIN] transfers its nitrogen atom to triphenylphosphine to give quantitatively the bis(triphenylphosphane)iminium cation [Ph3PNPPh3]+. A intermediate can be prepared by the reaction of a single molecule of triphenylphosphine with the polyoxometalate, the iminophosphorate derivative (n Bu4N)3[PW11O39RuV{NPPh3}]. The reactivity of the latter species has been investigated to complete the general scheme of the nitrogen transfer reaction. By addition of one equivalent of hydroxide, [PW11O39RuIII{N(OH)PPh3}]4- is obtained. The reaction can be reversed by the addition of one proton. The phosphinoxime derivative [PW11O39RuIII{N(OH)PPh3}]4- can be prepared in solution, but is unstable. It decomposes to yield quantitatively (n Bu4N)4[PW11O39RuIII{OPPh3}]. All those species have been thoroughly characterized by mass spectrometry, paramagnetic 31P NMR, IR, Raman, UV-visible, XANES and EXAFS spectroscopies

Keywords: Anions; Extended X-ray absorption fine structure; Oxidation state; Reaction products; Ruthenium

Domains: Chemical Sciences

Claire Besson, Yurii Geletii, Françoise Villain, Richard Villanneau, Craig Hill, et al.. Nitrogen-Atom Transfer from [PW 11 O 39 Ru VI N] 4− to PPh 3. Inorganic Chemistry, 2009, 48 (19), pp.9436-9443. ⟨10.1021/ic901345u⟩. ⟨hal-04564860⟩