Cracking the Dumbbell – from (NO)4[Pt2(SO4)5] to (NO)2[Pt(S2O7)3] by Oxidation with SO312. Issue 6 (10th March 2015)

• Record Type: Journal Article
• Authors: Bruns, Jörn; Niehaus, Oliver; Pöttgen, Rainer; Wickleder, Mathias S.
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 641:Issue 6(2015)
• Page Start: 1002
• Page End: 1008
• Publication Date: 2015-03-10
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201400600
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The reaction of elemental platinum, oleum (65 % SO<sub>3</sub>), and fuming nitric acid in sealed glass ampoules at 350 °C yielded orange single crystals of (NO)<sub>4</sub>[Pt<sub>2</sub>(SO<sub>4</sub>)<sub>5</sub>] [triclinic, <italic>P</italic><inline-formula><alternatives><tex-math notation="tex"><![CDATA[$\bar{1}$]]></tex-math><inline-graphic xlink:href="ark:/27927/pgjng7rd7n" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /></alternatives></inline-formula>, <italic>Z</italic> = 4, <italic>a</italic> = 977.41(3) pm, <italic>b</italic> = 1318.37(4) pm, <italic>c</italic> = 1511.47(5) pm, <italic>α</italic> = 105.218(1)°, <italic>β</italic> = 95.042(1)°, <italic>γ</italic> = 102.293(1)°, <italic>V</italic> = 1814.80(1)<bold>·</bold>10<sup>6</sup> pm<sup>3</sup>]. The crystal structure contains dumbbell shaped [Pt<sub>2</sub>] moieties surrounded by four chelating sulfate anions, forming the so‐called paddlewheel motif. The paddlewheels are connected via two terminal monodentate sulfate anions to infinite anionic chains. Charge compensation is achieved by nitrosylium cations. The reaction of (NO)<sub>4</sub>[Pt<sub>2</sub>(SO<sub>4</sub>)<sub>5</sub>] with neat SO<sub>3</sub> in sealed glass ampoules at 120 °C yielded yellow single crystals of the <italic>tris</italic>‐(disulfato)‐platinate(IV) (NO)<sub>2</sub>[Pt(S<sub>2</sub>O<sub>7</sub>)<sub>3</sub>] [triclinic, <italic>P</italic><inline-formula><alternatives><tex-math notation="tex"><![CDATA[$\bar{1}$]]></tex-math><inline-graphic xlink:href="ark:/27927/pgjng7rd85" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /></alternatives></inline-formula>, <italic>Z</italic> = 2, <italic>a</italic> = 893.20(4) pm, <italic>b</italic> = 1093.25(4) pm, <italic>c</italic> = 1098.63(4) pm, <italic>α</italic> = 62.329(2)°, <italic>β</italic> = 69.107(2)°, <italic>γ</italic> = 69.654(2)°, <italic>V</italic> = 865.88(6)<bold>·</bold>10<sup>6</sup> pm<sup>3</sup>]. In the structure of (NO)<sub>2</sub>[Pt(S<sub>2</sub>O<sub>7</sub>)<sub>3</sub>] the platinum atoms are coordinated by three bidentate chelating disulfate anions forming an octahedral coordination sphere of oxygen atoms around the platinum atom. Charge compensation is achieved by nitrosylium cations. The thermal behavior of both compounds was monitored by TG/DSC measurements. Magnetic susceptibility measurements on (NO)<sub>2</sub>[Pt(S<sub>2</sub>O<sub>7</sub>)<sub>3</sub>] revealed diamagnetism, proving the electronic d<sup>6</sup> low‐spin configuration of the Pt<sup>4+</sup> ion.</p> </abstract>