Nitrogen-atom transfer from [PW11O39Ru(VI)N]4- to PPh3.
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.
Besson
Claire
C
Institut parisien de chimie moléculaire, UMR 7071, Case courier 42, UPMC univ Paris 06, 4 place Jussieu, 75252 Paris Cedex, France.
Geletii
Yurii V
YV
Villain
Françoise
F
Villanneau
Richard
R
Hill
Craig L
CL
Proust
Anna
A