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 [PW₁₁O₃₉Ru^II(NO)]^4- (1^4-) was obtained in high yield by reaction of [Ru(NO)Cl₅]^2- with [PW₁₁O₃₉]^7- and characterized by multinuclear NMR, cyclic voltammetry, IR spectroscopy, and electrospray ionization mass spectrometry (ESI-MS). The intrinsic reactivity of the {RuNO} site in 1^4- 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 [PW₁₁O₃₉Ru^III(H₂O)]^4- (2^4-) in aqueous solution. In the reaction with hydroxylamine, an intermediate with coordinated dinitrogen has been detected. An easy access to the NH₃-coordinated [PW₁₁O₃₉RuNH₃]^4- (3^4-) complex was achieved upon reduction of 1^4- with Sn²⁺ in water.