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Biomimetic Water Oxidation Catalyzed by a Binuclear Ruthenium (IV) Nitrido-Chloride Complex with Lithium Counter-Cations

1
Institute of Problems of Chemical Physics of RAS, Moscow Region, Academician Semenov Ave., 1, 142432 Chernogolovka, Russia
2
Faculty of fundamental physical and chemical engineering, Lomonosov Moscow State University, GSP-1, 1 Leninskiye Gory, 119991 Moscow, Russia
*
Authors to whom correspondence should be addressed.
Biomimetics 2020, 5(1), 3; https://doi.org/10.3390/biomimetics5010003
Received: 29 June 2019 / Revised: 25 December 2019 / Accepted: 26 December 2019 / Published: 16 January 2020
The lithium salt of the binuclear nitrido complex of ruthenium (IV) Li3(Ru2NCl8·2H2O) was synthesized. Using UV spectroscopy and voltammetry, we studied complex behavior in aqueous solutions. It was found that in dilute solutions of this compound, Cl ions are replaced by H2O molecules, and the intra-sphere redox reaction between Ru (IV) and H2O, as well as the oxidation of water with the formation of oxygen and the acidic dissociation of coordinated water molecules also have been taking place. It was established by IR spectroscopy and ESI mass spectrometric analysis that not only the binuclear structure of the complex is preserved in acidic solutions, but also its dimerization product into the tetra-ruthenium dinitrido cluster Ru4N2O5+, which is a catalyst for the water oxidation reaction. The activity of the catalyst was TOF = 0.33 s−1, TON = 304. View Full-Text
Keywords: biomimetic catalysis; water oxidation; oxygen; binuclear nitrido complex Ru(IV) with lithium counter-cations biomimetic catalysis; water oxidation; oxygen; binuclear nitrido complex Ru(IV) with lithium counter-cations
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Dzhabieva, Z.M.; Shilov, G.V.; Avdeeva, L.V.; Dobrygin, V.V.; Tkachenko, V.Y.; Dzhabiev, T.S. Biomimetic Water Oxidation Catalyzed by a Binuclear Ruthenium (IV) Nitrido-Chloride Complex with Lithium Counter-Cations. Biomimetics 2020, 5, 3.

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