Oxidizing Elemental Platinum with Oleum under Harsh Conditions: The Unique Tris(disulfato)platinate(IV) [Pt(S2O7)3]2− Anion |
| |
Authors: | Jörn Bruns Prof?Dr Thorsten Klüner Prof?Dr Mathias S Wickleder |
| |
Institution: | Carl von Ossietzky University of Oldenburg, Institute of Chemistry, Carl‐von‐Ossietzky‐Strasse 9–11, 26129 Oldenburg (Germany), Fax: (+49)?441‐798‐3352 |
| |
Abstract: | For the first time, direct oxidation of elemental platinum by a mineral acid to its tetravalent state was observed in course of the reaction of platinum with oleum (65 % SO3) in the presence of barium carbonate. The reaction has been carried out in torch‐sealed glass ampoules at 160 °C and gave yellow single crystals of BaPt(S2O7)3](H2SO4)0.5(H2S2O7)0.5 (triclinic, P$\bar 1$ , Z=2, a=992.05(2), b=1069.07(3), c=1114.22(3) pm, α=69.49(7), β=72.96(2), γ=72.93(1)°, V=1033.95(5) Å3). The structure of BaPt(S2O7)3](H2SO4)0.5(H2S2O7)0.5 exhibits the unique tris‐(disulfato)‐platinate anion Pt(S2O7)3]2? with three chelating disulfate groups coordinated to the platinum atom. Charge balance is achieved by the Ba2+ ions, which are coordinated by (S2O7)2? groups from the platinate complex and by disordered sulfuric acids and disulfuric acid molecules. Thermal decomposition of the bulk material revealed elemental platinum and barium sulfate as decomposition residual. |
| |
Keywords: | electronic structure calculations oleum platinum polysulfates structure elucidation |
|
|