Oxidizing Elemental Platinum with Oleum under Harsh Conditions: The Unique Tris(disulfato)platinate(IV) [Pt(S2O7)3]2− Anion. Issue 24 (9th May 2014)

• Record Type: Journal Article
• Authors: Bruns, Jörn; Klüner, Thorsten; Wickleder, Mathias S.
• Is Part Of: Chemistry. Volume 20:Issue 24(2014)
• Page Start: 7222
• Page End: 7227
• Publication Date: 2014-05-09
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201402086
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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 % SO<sub>3</sub>) 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 Ba[Pt(S<sub>2</sub>O<sub>7</sub>)<sub>3</sub>](H<sub>2</sub>SO<sub>4</sub>)<sub>0.5</sub>(H<sub>2</sub>S<sub>2</sub>O<sub>7</sub>)<sub>0.5</sub> (triclinic, <italic>P</italic><tex-math notation="tex"><![CDATA[$\bar 1$]]></tex-math><inline-graphic xlink:href="ark:/27927/pghh52v0f4" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" />, <italic>Z</italic>=2, <italic>a</italic>=992.05(2), <italic>b</italic>=1069.07(3), <italic>c</italic>=1114.22(3) pm, <italic>α</italic>=69.49(7), <italic>β</italic>=72.96(2), <italic>γ</italic>=72.93(1)°, <italic>V</italic>=1033.95(5) Å<sup>3</sup>). The structure of Ba[Pt(S<sub>2</sub>O<sub>7</sub>)<sub>3</sub>](H<sub>2</sub>SO<sub>4</sub>)<sub>0.5</sub>(H<sub>2</sub>S<sub>2</sub>O<sub>7</sub>)<sub>0.5</sub> exhibits the unique <italic>tris</italic>‐(disulfato)‐platinate anion [Pt(S<sub>2</sub>O<sub>7</sub>)<sub>3</sub>]<sup>2−</sup> with three chelating disulfate groups coordinated to the platinum atom. Charge balance is achieved by the Ba<sup>2+</sup> ions, which are coordinated by (S<sub>2</sub>O<sub>7</sub>)<sup>2−</sup> 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.</p> </abstract>