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The article of NIIC researches Vasilchenko D.B., Tkachev S.V, Baidina I.A. and Korenev S.V is published in Inorganic Chemistry (IF 4.593)
«Speciation of Platinum(IV) in Nitric Acid Solutions»Inorg. Chem., 2013, V. 52(18), P. 10532–10541DOI: 10.1021/ic401499j
NMR spectrum of H2[Pt(OH)6] in nitric acid solution, signals of mono- and polynuclear species of Pt(IV) are shown
In the work the speciation of platinum(IV) ions in nitric acid (6–15.8 M) solutions of H2[Pt(OH)6] has been studied by 195Pt NMR and Raman spectroscopy. Series of aqua-hydroxo-nitrato complexes [Pt(L)x(NO3)6–x] (L = H2O or OH–; x = 0, ..., 6) were found to exist in such solutions. Mononuclear hexanitratoplatinates(IV) have been isolated in solid state in substantial yield as pyridinium salt (PyH)2[Pt(NO3)6] and characterized by single-crystal X-ray diffraction. Aging of the platinum nitric acid solutions for more than 5–6 h results in oligomerization of [Pt(L)x(NO3)6–x] species and the formation of oligonuclear aqua-hydroxo-nitrato complexes with OH– and NO3– bridging ligands. Oligomeric platinum(IV) complexes with two and four nuclei were unambiguously detected by NMR on195Pt -enriched samples. Oligomers with even higher nuclearity were also detected. Dimeric anions [Pt2(μ-OH)2(NO3)8]2– have been isolated as single crystals of tetramethylammonium salt and characterized by X-ray diffraction.