Synthesis and Characterization of the Keggin-Type Ruthenium-Nitrido Derivative [PW11O39{RuN}]4- and Evidence of Its Electrophilic Reactivity
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- 作者：Vanina Lahootun ; Claire Besson ; Richard Villanneau ; Franç ; oise Villain ; Lise-Marie Chamoreau ; Kamal Boubekeur ; Sé ; bastien Blanchard ; René ; Thouvenot ; Anna Proust
- 刊名：Journal of the American Chemical Society
- 出版年：2007
- 出版时间：June 6, 2007
- 年：2007
- 卷：129
- 期：22
- 页码：7127 - 7135
- 全文大小：227K
- 年卷期：v.129,no.22(June 6, 2007)
- ISSN：1520-5126
文摘
The ruthenium-nitrido POM derivative [PW11O39{RuVIN}]4- has been synthesized by reactionbetween [PW11O39]7- and [RuVINCl5]2- or [RuVINCl4]-. Its molecular structure has been confirmed frommultinuclear 31P and 183W NMR spectroscopy together with an EXAFS study, while the oxidation state ofthe ruthenium bearing the nitrido ligand has been inferred both from 183W NMR and XANES analysis at theRu-K edge. The potential of [PW11O39{RuVIN}]4- in N-atom transfer reactions has been demonstrated throughreaction with triphenylphosphine, which ultimately leads to the release of the bis(triphenylphosphane)iminium cation [PPh3=N=PPh3]+ through several intermediates, among which the phosphoraniminatoderivative [PW11O39{RuVNPh3}]3- has been structurally characterized. Its unusual oxidation state is inaccordance with its EPR spectrum.