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