Ba2[Pd(HS2O7)2(S3O10)2]: A Heteroleptic Polysulfatopalladate. Issue 6 (16th April 2014)

• Record Type: Journal Article
• Authors: Bruns, Jörn; Klüner, Thorsten; Wickleder, Mathias S.
• Is Part Of: Chemistry, an Asian journal. Volume 9:Issue 6(2014:Jun.)
• Page Start: 1594
• Page End: 1600
• Publication Date: 2014-04-16
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201402067
• Languages: English
• ISSNs: 1861-4728

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The oxidation of elemental palladium with oleum (65 % SO<sub>3</sub>) in the presence of barium carbonate in torch‐sealed glass ampoules at 180 °C leads to yellow single crystals of the heteroleptic palladate Ba<sub>2</sub>[Pd(HS<sub>2</sub>O<sub>7</sub>)<sub>2</sub>(S<sub>3</sub>O<sub>10</sub>)<sub>2</sub>] (triclinic, <italic>P</italic><tex-math notation="tex"><![CDATA[$\bar 1$]]></tex-math><inline-graphic xlink:href="ark:/27927/pgh2sx8rcs" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" />; <italic>Z</italic>=1; <italic>a</italic>=884.18(3), <italic>b</italic>=927.68(3), <italic>c</italic>=938.77(4) pm; <italic>α</italic>=60.473(1), <italic>β</italic>=80.266(2), <italic>γ</italic>=87.746(2)°). The crystal structure shows the Pd<sup>2+</sup> ions in a square‐planar coordination of oxygen atoms of two hydrogendisulfate as well as of two trisulfate anions. The compound is the first example of the rarely seen S<sub>3</sub>O<sub>10</sub><sup>2−</sup> and HS<sub>2</sub>O<sub>7</sub><sup>−</sup> anions acting as ligands in a complex anion and, moreover, the first heteroleptic polysulfatometallate known so far. The complex formation leads to a stabilization of the trisulfate anion relative to its uncoordinated congener. Ba<sub>2</sub>[Pd(HS<sub>2</sub>O<sub>7</sub>)<sub>2</sub>(S<sub>3</sub>O<sub>10</sub>)<sub>2</sub>] has been further characterized by vibrational spectroscopy and quantum chemical calculations. Thermal analyses by means of thermogravimetric/differential thermal analysis (TG/DTA) measurements show that the compound decomposes to yield elemental palladium and BaSO<sub>4</sub>.</p> </abstract>