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Ostvald, Roman V.
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article
Reactions of KBrF4 with platinum metals
Abstract
<p>The reaction of various platinum metals (M = Ru, Os, Rh, Ir, Pd, Pt) with KBrF<sub>4</sub> was investigated upon heating their mixtures to 400 °C. The formation of potassium fluorido platinum metallates in oxidation states +4 or +5, K<sub>2</sub>MF<sub>6</sub> or KMF<sub>6</sub>, respectively, was observed in all cases. The obtained products were tested for their stability in water. Depending on the platinum metal, they were either stable, were reduced to the oxidation state +4, or were hydrolyzed to so far unidentified phases. K<sub>2</sub>RuF<sub>6</sub>, K<sub>2</sub>OsF<sub>6</sub>, α-K<sub>2</sub>PdF<sub>6</sub>, β-K<sub>2</sub>PdF<sub>6</sub>, which were previously only poorly characterized, were structurally reinvestigated by single crystal or powder X-ray diffraction, Raman and IR spectroscopy. The three former compounds crystallize isotypic in the trigonal, the latter in the hexagonal crystal system. The α→β phase transition of K<sub>2</sub>PdF<sub>6</sub> was found to be reconstructive. Quantum chemical calculations were used to investigate the crystal structures.</p>