Abstract
Stabilization of Cu2+ ions in concentrated aqueous ammonia solutions of copper nitrate in a wide range of ammonium ion concentrations has been studied by EPR and electronic absorption spectroscopy. Three types of Cu2+ associates with different types of orbital ordering have been identified. The ammonium ion concentration in a solution has a decisive effect on the type of orbital ordering of Cu2+ ions in associates. In all cases, Cu2+ ordering in associates is caused by the existence of bridging OH groups in the axial and equatorial positions of [Cu(NH3) n (H2O)6 − n ]2+ complexes (n < 6). At a high concentration of ammonium ions, weakly bound associates of tetramminecopper with the \(d_{x^2 - y^2 }\) ground state are formed. In solutions with low ammonium concentrations, bulky associates with the \(d_{y^2 }\) and \(d_{x^2 - z^2 }\) ground states and associates of Cu2+ ions with the \(d_{x^2 - y^2 }\) ground state with hydroxyl groups in the equatorial plane and axial water molecules are formed.
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Original Russian Text © V.F. Anufrienko, R.A. Shutilov, G.A. Zenkovets, V.Yu. Gavrilov, N.T. Vasenin, A.A. Shubin, T.V. Larina, A.V. Zhuzhgov, Z.R. Ismagilov, V.N. Parmon, 2012, published in Zhurnal Neorganicheskoi Khimii, 2012, Vol. 57, No. 9, pp. 1368–1373.
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Anufrienko, V.F., Shutilov, R.A., Zenkovets, G.A. et al. The state of Cu2+ ions in concentrated aqueous ammonia solutions of copper nitrate. Russ. J. Inorg. Chem. 57, 1285–1290 (2012). https://doi.org/10.1134/S0036023612090033
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DOI: https://doi.org/10.1134/S0036023612090033