An octameric fluoridopalladate(IV) [Pd8F36]4− anion in KPd2F9 revealed by 3D electron diffraction

The chemistry of fluoridopalladates(IV) is mainly limited to salts containing the discrete [PdF 6 ] 2− anion. Reaction of K 2 PdF 6 with AsF 5 in anhydrous HF results in the removal of KF as KAsF 6 and the formation of KPd 2 F 9 . The product was characterized by Raman spectroscopy, powder X-ray diffraction and 3D electron diffraction (3D ED). Crystal structure elucidation revealed a rare example of an oligomeric fluoridopalladate(IV) anion, namely the cube-shaped octameric [Pd 8 F 36 ] 4− species. Raman spectroscopic investigations of analogous reactions involving Rb 2 PdF 6 and Cs 2 PdF 6 indicate that related fluoridopalladate(IV) species also likely formed.