Anhydrous perchlorato complexes of palladium(II):: Pd(ClO4)2, (ClO2)2Pd(ClO4)4, and (NO2)2Pd(ClO4)4.: Syntheses and structural analyses

Chlorine trioxide (Cl2O6) reacts with PdCl2 to yield "ClO2Pd(ClO4)(3)" which is, in fact, an equimolar mixture of Pd(ClO4)(2) and (ClO2)(2)Pd(ClO4)(4). The chloryl salt decomposes under vacuum to give Pd(ClO4)(2). (NO2)(2)Pd(ClO4)(4).0.5 NO2ClO4 is prepared using Pd(NO3)(2).0.5 (H2O, HNO3) as the starting salt. Excess NO2ClO4 sublimes easily and pure (NO2)(2)Pd(ClO4)(4) is obtained. Pd(ClO4)(2) and (NO2)(2)Pd(ClO4)(4) crystallize poorly; however, a P2(1)/m space group is proposed for the latter. A complete assignment of vibrational modes, and DFT calculations, show that Pd(ClO4)(2) is monomeric with chelating bidentate [ClO4] groups and Pd is in a square planar environment. In nitryl and chloryl salts, individual anions (Pd(ClO4)(4)(2-)), where unidentate [ClO4] groups interact partially with the cation or the Pd core, were characterized.