New {RuNO} Polyoxometalate [PW11O39RuII(NO)]4-: Synthesis and Reactivity

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• 作者：Maxim N. Sokolov ; Sergey A. Adonin ; Dmitry A. Mainichev ; Pavel L. Sinkevich ; C. Vicent ; Nikolay B. Kompankov ; Artem L. Gushchin ; V.A. Nadolinny ; Vladimir P. Fedin
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：August 19, 2013
• 年：2013
• 卷：52
• 期：16
• 页码：9675-9682
• 全文大小：429K
• 年卷期：v.52,no.16(August 19, 2013)
• ISSN：1520-510X

文摘

New Ru-containing polyoxometalate [PW₁₁O₃₉Rup>IIp>(NO)]p>4-p> (1p>4-p>) was obtained in high yield by reaction of [Ru(NO)Cl₅]p>2-p> with [PW₁₁O₃₉]p>7-p> and characterized by multinuclear NMR, cyclic voltammetry, IR spectroscopy, and electrospray ionization mass spectrometry (ESI-MS). The intrinsic reactivity of the {RuNO} site in 1p>4-p> toward various reagents has been studied using a versatile and simple ESI tandem mass spectrometric methodology for identification of the L attached at the Ru site; this approach relies on the preferential liberation of the L ligands attached at the Ru sites upon mass-selecting desired intermediates and subsequent promotion of their fragmentation. Reactions with both hydrazine and hydroxylamine lead to elimination of the nitroso group and quantitative formation of [PW₁₁O₃₉Rup>IIIp>(H₂O)]p>4-p> (2p>4-p>) in aqueous solution. In the reaction with hydroxylamine, an intermediate with coordinated dinitrogen has been detected. An easy access to the NH₃-coordinated [PW₁₁O₃₉RuNH₃]p>4-p> (3p>4-p>) complex was achieved upon reduction of 1p>4-p> with Snp>2+p> in water.