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

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journal contribution
posted on 19.08.2013, 00:00 by 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
New Ru-containing polyoxometalate [PW11O39RuII(NO)]4‑ (14‑) 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 14‑ 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 [PW11O39RuIII(H2O)]4‑ (24‑) 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‑ (34‑) complex was achieved upon reduction of 14‑ with Sn2+ in water.