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Pd(SeO 3 ), Pd(SeO 4 ), and Pd(Se 2 O 5 ): The First Palladium Oxoselenates
Author(s) -
Arndt Annika,
Wickleder Mathias S.
Publication year - 2007
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200700321
Subject(s) - chemistry , palladium , crystallography , ion , denticity , crystal structure , single crystal , lone pair , selenium , catalysis , molecule , biochemistry , organic chemistry
Depending on the reaction conditions, the reaction of elemental palladium with H 2 SeO 4 in sealed glass tubes at 350 °C leads to red single crystals of Pd(SeO 3 ) [ C 2/ m , Z = 4, a = 6.788(2), b = 7.030(2), c = 7.008(2) Å, β = 118.09(3)°] or to yellow‐orange single crystals of Pd(SeO 4 ) [ C 2/ c , Z = 4, a = 8.171(1), b = 5.286(1), c = 8.115(1) Å, β = 94.54(1)°]. Yellow‐orange single crystals of Pd(Se 2 O 5 ) [ I 2/ a , Z = 4, a = 7.212(1), b = 5.569(1), c = 12.177(3) Å, β = 106.84(2)°] are obtained when SeO 3 is added to the reaction mixture. X‐ray single‐crystal diffraction shows that Pd(SeO 3 ) consists of layers that are formed by square‐planar coordinated Pd 2+ ions and pyramidal SeO 3 2– groups. These layers are held together by weak interactions involving the lone electron pairs of the selenium atoms. The Se–O distances within the selenite ion are different (1.69 and 1.76 Å), in accordance with the different attachment of the oxygen atoms to the Pd 2+ ions. The square‐planar [PdO 4 ] units in the crystal structure of Pd(SeO 4 ) are linked by tetrahedral SeO 4 2– ions into a three‐dimensional network. These anions act as monodentate ligands towards the Pd 2+ ions, with Se–O distances of around 1.65 Å. The Pd 2+ ions in the crystal structure of Pd(Se 2 O 5 ) are coordinated by two chelating diselenite ions. The Se 2 O 5 2– ions link the palladium ions into corrugated chains, which are held together by weak interactions only. The IR spectra of these compounds display the typical bands for oxoselenate anions.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)