Oxoanionic Noble Metal Compounds from Fuming Nitric Acid: The Palladium Examples Pd(NO3)2 and Pd(CH3SO3)2. Issue 3 (27th November 2014)

• Record Type: Journal Article
• Authors: Bruns, Jörn; Klüner, Thorsten; Wickleder, Mathias S.
• Is Part Of: Chemistry. Volume 21:Issue 3(2015)
• Page Start: 1294
• Page End: 1301
• Publication Date: 2014-11-27
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201405355
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The oxidation of elemental palladium at 100 °C in a mixture of fuming nitric acid and a pyridine‐SO<sub>3</sub> complex leads to the anhydrous nitrate Pd(NO<sub>3</sub>)<sub>2</sub> (monoclinic, <italic>P</italic>2<sub>1</sub>/<italic>n</italic>, <italic>Z</italic>=2, <italic>a</italic>=469.12(3) pm, <italic>b</italic>=593.89(3) pm, <italic>c</italic>=805.72(4) pm, <italic>β</italic>=105.989(3)°, <italic>V</italic>=215.79(2) Å<sup>3</sup>). The Pd<sup>2+</sup> ions are in square‐planar coordination with four monodentate nitrate groups which are connected to further palladium atoms, leading to a layer structure. The reaction of elemental palladium with a mixture of fuming nitric acid and methanesulfonic acid at 120 °C leads to single crystals of Pd(CH<sub>3</sub>SO<sub>3</sub>)<sub>2</sub> (monoclinic, <italic>P</italic>2<sub>1</sub>/<italic>n</italic>, <italic>Z</italic>=2, <italic>a</italic>=480.44(1) pm, <italic>b</italic>=1085.53(3) pm, <italic>c</italic>=739.78(2) pm, <italic>β</italic>=102.785(1)°, <italic>V</italic>=376.254(17) Å<sup>3</sup>). Also in this structure the Pd<sup>2+</sup> ions are in square‐planar coordination with four monodentate anions; however, the connection to adjacent palladium atoms leads to a chain‐type structure. The thermal decomposition of the compounds has been investigated by means of DSC/TG measurements. Furthermore, IR and Raman spectra have been recorded, and an assignment of the observed vibrational frequencies has been carried out based on theoretical investigations.</p> </abstract>