Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Salts containing new cyanido(fluorido)phosphate anions of the general formula [PF<jats:sub>6−<jats:italic>n</jats:italic></jats:sub>(CN)<jats:sub><jats:italic>n</jats:italic></jats:sub>]<jats:sup>−</jats:sup> (<jats:italic>n</jats:italic>=1–4) were synthesized by a very mild Lewis‐acid‐catalyzed synthetic protocol and fully characterized. All [PF<jats:sub>6−<jats:italic>n</jats:italic></jats:sub>(CN)<jats:sub><jats:italic>n</jats:italic></jats:sub>]<jats:sup>−</jats:sup> (<jats:italic>n</jats:italic>=1–4) salts could be isolated on a preparative scale. It was also possible to detect the [PF(CN)<jats:sub>5</jats:sub>]<jats:sup>−</jats:sup> but not the [P(CN)<jats:sub>6</jats:sub>]<jats:sup>−</jats:sup> anion. The best results with respect to purity, yield, and low cost were obtained when the F<jats:sup>−</jats:sup>/CN<jats:sup>−</jats:sup> substitution reactions were carried out in ionic liquids.</jats:p>