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Oxoanionic Noble Metal Compounds from Fuming Nitric Acid: The Palladium Examples Pd(NO 3 ) 2 and Pd(CH 3 SO 3 ) 2
Author(s) -
Bruns Jörn,
Klüner Thorsten,
Wickleder Mathias S.
Publication year - 2015
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.201405355
Subject(s) - palladium , nitric acid , denticity , chemistry , monoclinic crystal system , pyridine , thermal decomposition , inorganic chemistry , infrared spectroscopy , metal , crystallography , platinum , crystal structure , medicinal chemistry , organic chemistry , catalysis
The oxidation of elemental palladium at 100 °C in a mixture of fuming nitric acid and a pyridine‐SO 3 complex leads to the anhydrous nitrate Pd(NO 3 ) 2 (monoclinic, P 2 1 / n , Z =2, a =469.12(3) pm, b =593.89(3) pm, c =805.72(4) pm, β =105.989(3)°, V =215.79(2) Å 3 ). The Pd 2+ 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 3 SO 3 ) 2 (monoclinic, P 2 1 / n , Z =2, a =480.44(1) pm, b =1085.53(3) pm, c =739.78(2) pm, β =102.785(1)°, V =376.254(17) Å 3 ). Also in this structure the Pd 2+ 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.