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- Title
Cracking the Dumbbell - from (NO)<sub>4</sub>[Pt<sub>2</sub>(SO<sub>4</sub>)<sub>5</sub>] to (NO)<sub>2</sub>[Pt(S<sub>2</sub>O<sub>7</sub>)<sub>3</sub>] by Oxidation with SO<sub>3</sub>.
- Authors
Bruns, Jörn; Niehaus, Oliver; Pöttgen, Rainer; Wickleder, Mathias S.
- Abstract
The reaction of elemental platinum, oleum (65 % SO3), and fuming nitric acid in sealed glass ampoules at 350 °C yielded orange single crystals of (NO)4[Pt2(SO4)5] [triclinic, P $\bar{1}$, Z = 4, a = 977.41(3) pm, b = 1318.37(4) pm, c = 1511.47(5) pm, α = 105.218(1)°, β = 95.042(1)°, γ = 102.293(1)°, V = 1814.80(1) ·106 pm3]. The crystal structure contains dumbbell shaped [Pt2] 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)4[Pt2(SO4)5] with neat SO3 in sealed glass ampoules at 120 °C yielded yellow single crystals of the tris-(disulfato)-platinate(IV) (NO)2[Pt(S2O7)3] [triclinic, P $\bar{1}$, Z = 2, a = 893.20(4) pm, b = 1093.25(4) pm, c = 1098.63(4) pm, α = 62.329(2)°, β = 69.107(2)°, γ = 69.654(2)°, V = 865.88(6) ·106 pm3]. In the structure of (NO)2[Pt(S2O7)3] 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)2[Pt(S2O7)3] revealed diamagnetism, proving the electronic d6 low-spin configuration of the Pt4+ ion.
- Subjects
SINGLE crystals; CRYSTAL structure; THERMAL analysis; SULFURIC acid; OXYGEN atom transfer reactions
- Publication
Zeitschrift für Anorganische und Allgemeine Chemie, 2015, Vol 641, Issue 6, p1002
- ISSN
0044-2313
- Publication type
Article
- DOI
10.1002/zaac.201400600