Lahootun Vanina, Besson Claire, Villanneau Richard, Villain Françoise, Chamoreau Lise-Marie, Boubekeur Kamal, Blanchard Sébastien, Thouvenot René, Proust Anna
Laboratoire de Chimie Inorganique et Matériaux Moléculaires, UMR CNRS 7071, Université Pierre et Marie Curie-Paris6, Institut de Chimie Moléculaire FR2769, 4 Place Jussieu, Case 42, 75252 Paris Cedex 05, France.
J Am Chem Soc. 2007 Jun 6;129(22):7127-35. doi: 10.1021/ja071137t. Epub 2007 May 12.
The ruthenium-nitrido POM derivative [PW11O39{RuVIN}]4- has been synthesized by reaction between [PW11O39]7- and [RuVINCl5]2- or [RuVINCl4]-. Its molecular structure has been confirmed from multinuclear 31P and 183W NMR spectroscopy together with an EXAFS study, while the oxidation state of the ruthenium bearing the nitrido ligand has been inferred both from 183W NMR and XANES analysis at the Ru-K edge. The potential of [PW11O39{RuVIN}]4- in N-atom transfer reactions has been demonstrated through reaction with triphenylphosphine, which ultimately leads to the release of the bis(triphenylphosphane)iminium cation [PPh3=N=PPh3]+ through several intermediates, among which the phosphoraniminato derivative [PW11O39{RuVNPh3}]3- has been structurally characterized. Its unusual oxidation state is in accordance with its EPR spectrum.
钌-氮杂多金属氧酸盐衍生物[PW11O39{RuVIN}]4-是通过[PW11O39]7-与[RuVINCl5]2-或[RuVINCl4]-反应合成的。其分子结构已通过多核31P和183W核磁共振光谱以及扩展X射线吸收精细结构（EXAFS）研究得到证实，而带有氮杂配体的钌的氧化态则通过183W核磁共振和Ru-K边的X射线吸收近边结构（XANES）分析推断得出。[PW11O39{RuVIN}]4-在氮原子转移反应中的潜力已通过与三苯基膦反应得到证明，该反应最终通过几种中间体导致双（三苯基膦）亚胺阳离子[PPh3=N=PPh3]+的释放，其中磷亚胺基衍生物[PW11O39{RuVNPh3}]3-已通过结构表征。其不寻常的氧化态与其电子顺磁共振（EPR）光谱一致。
