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Nitrogen-Atom Transfer from [PW11O39RuVIN]4- to PPh3.

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Title: Nitrogen-Atom Transfer from [PW11O39RuVIN]4- to PPh3.
Authors: Besson, Claire1,2, Geletii, Yurii V.2, Villain, Françoise1,3, Villanneau, Richard1, Hill, Craig L.2, Proust, Anna1 anna.proust@upmc.fr
Source: Inorganic Chemistry. 10/5/2009, Vol. 48 Issue 19, p9436-9443. 8p. 7 Graphs.
Subjects: Nitrogen isotopes, Intermediates (Chemistry), Chemical reactions, Polyoxometalates, Hydroxides, Mass spectrometry, Ruthenium compounds
Abstract: The nitrido derivative (n-Bu4N)4[PW11O39RuVIN] transfers its nitrogen atom to triphenylphosphine to give quantitatively the bis(triphenylphosphane)iminium cation [Ph3PNPPh3]+. An intermediate can be prepared by the reaction of a single molecule of triphenylphosphine with the polyoxometalate, the iminophosphorane 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 the addition oil equiv of hydroxide, PW11O39RuIIIN(OH)PPh3]4- is obtained. The reaction can be reversed by the addition of one proton. The phosphinoxime derivative [PW11O39RuIII(N](OH)NPPh3)]4- can be prepared in solution but is unstable. II decomposes to yield quantitatively (n-Bu4N)4[PW11O39RuIII(OPPh3)]. All of those species have been thoroughly characterized by mass spectrometry, paramagnetic 31P NMR, Itt, Roman, UV-sisible, XANES, and EXAFS spectroscopies. [ABSTRACT FROM AUTHOR]
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Abstract:The nitrido derivative (n-Bu4N)4[PW11O39RuVIN] transfers its nitrogen atom to triphenylphosphine to give quantitatively the bis(triphenylphosphane)iminium cation [Ph3PNPPh3]+. An intermediate can be prepared by the reaction of a single molecule of triphenylphosphine with the polyoxometalate, the iminophosphorane 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 the addition oil equiv of hydroxide, PW11O39RuIIIN(OH)PPh3]4- is obtained. The reaction can be reversed by the addition of one proton. The phosphinoxime derivative [PW11O39RuIII(N](OH)NPPh3)]4- can be prepared in solution but is unstable. II decomposes to yield quantitatively (n-Bu4N)4[PW11O39RuIII(OPPh3)]. All of those species have been thoroughly characterized by mass spectrometry, paramagnetic 31P NMR, Itt, Roman, UV-sisible, XANES, and EXAFS spectroscopies. [ABSTRACT FROM AUTHOR]
ISSN:00201669
DOI:10.1021/ic901345u