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Oxidizing Elemental Platinum with Oleum under Harsh Conditions: The Unique Tris(disulfato)platinate(IV) [Pt(S 2 O 7 ) 3 ] 2− Anion
Author(s) -
Bruns Jörn,
Klüner Thorsten,
Wickleder Mathias S.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402086
Subject(s) - platinum , oleum , chemistry , inorganic chemistry , barium , thermal decomposition , sulfuric acid , decomposition , catalysis , organic chemistry , biochemistry
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 3 ) 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 2 O 7 ) 3 ](H 2 SO 4 ) 0.5 (H 2 S 2 O 7 ) 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) Å 3 ). The structure of Ba[Pt(S 2 O 7 ) 3 ](H 2 SO 4 ) 0.5 (H 2 S 2 O 7 ) 0.5 exhibits the unique tris ‐(disulfato)‐platinate anion [Pt(S 2 O 7 ) 3 ] 2− with three chelating disulfate groups coordinated to the platinum atom. Charge balance is achieved by the Ba 2+ ions, which are coordinated by (S 2 O 7 ) 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.