Palladium compounds with +III oxidation state
1985; Elsevier BV; Volume: 29; Issue: 1-2 Linguagem: Inglês
10.1016/s0022-1139(00)83274-1
ISSN1873-3328
AutoresA. Tressaud, S. Khaïroun, J. Grannec, J.M. Dance, Paul Hagenmuller,
Tópico(s)Crystal Structures and Properties
ResumoAbstract The trivalent oxidation state of palladium has been stabilized and unequivocally characterized in several fluoride series. NaPdF 4 , whose structure can be derived from the KBrF 4 type, is obtained under high pressure and is quenched back to ambient conditions. Elpasolite compounds of A 2 BPdF 6 formulation (A, B = alkali metal) are synthesized via solid state reactions. Between 200 and 500 K every A 2 BPdF 6 compound undergoes a tetragonal cubic phase transition. The ESR spectra are characteristic of a doublet ground state. The t 6 2g e 1 g configuration of Pd(+III) is stabilized versus the t 5 2g e 2 g high-spin alternative by an important Jahn-Teller splitting of the 2 E g state. In most cases ESR spectra are consistent with tetragonally elongated PdF 6 octahedra; an orthorhombic component occurs for Cs 2 KPdF 6 and Cs 2 RbPdF 6 . ESR spectra with tetragonal (a-K 2 NaPdF 6 ) and orthorhombic (b-Cs 2 KPdF 6 ) symmetries.
Referência(s)