title: Nitrogen-atom transfer from [PW11O39Ru(VI)N]4- to PPh3.
abstract: The nitrido derivative (n-Bu(4)N)(4)[PW(11)O(39)Ru(VI)N] transfers its nitrogen atom to triphenylphosphine to give quantitatively the bis(triphenylphosphane)iminium cation [Ph(3)PNPPh(3)](+). An intermediate can be prepared by the reaction of a single molecule of triphenylphosphine with the polyoxometalate, the iminophosphorane derivative (n-Bu(4)N)(3)[PW(11)O(39)Ru(V){NPPh(3)}]. The reactivity of the latter species has been investigated to complete the general scheme of the nitrogen-transfer reaction. By the addition of 1 equiv of hydroxide, [PW(11)O(39)Ru(III){N(OH)PPh(3)}](4-) is obtained. The reaction can be reversed by the addition of one proton. The phosphinoxime derivative [PW(11)O(39)Ru(III){N(OH)PPh(3)}](4-) can be prepared in solution but is unstable. It decomposes to yield quantitatively (n-Bu(4)N)(4)[PW(11)O(39)Ru(III){OPPh(3)}]. All of those species have been thoroughly characterized by mass spectrometry, paramagnetic (31)P NMR, IR, Raman, UV-visible, XANES, and EXAFS spectroscopies.
authors.affiliation: Institut parisien de chimie moléculaire, UMR 7071, Case courier 42, UPMC univ Paris 06, 4 place Jussieu, 75252 Paris Cedex, France.
authors.forename: Claire
authors.initials: C
authors.lastname: Besson
authors.forename: Yurii V
authors.initials: YV
authors.lastname: Geletii
authors.forename: Françoise
authors.initials: F
authors.lastname: Villain
authors.forename: Richard
authors.initials: R
authors.lastname: Villanneau
authors.forename: Craig L
authors.initials: CL
authors.lastname: Hill
authors.forename: Anna
authors.initials: A
authors.lastname: Proust