Tetrahedral [Pt(PF(3))(4)] reacts with H(+) to form trigonal bipyramidal [Pt(PF(3))(4)H](+). This in turn looses PF(3) to form square-planar [Pt(PF(3))(3)H](+). The complex [Pt(PF(3))(4)] can be oxidized with AsF(5) to form the square-planar complex, [Pt(PF(3))(4)](2+), which can be more conveniently obtained from PtF(4) and PF(3) in HF/SbF(5) solution. [Pt(PF(3))(4)](2+) reacts with F(-) in HF under cluster formation to [Pt(4)(PF(3))(8)H](+).

Platinum I 8300 Systematic Reactions of [Pt(PF3)4]. -New Pt-PF3 compounds are synthesized and characterized by single crystal XRD, NMR, IR, and Raman spectroscopy, and ab initio MP2 calculations. (III) crystallizes in the cubic space group I43m (Z = 2), (IV) in the orthorhombic space group Pmmn (Z = 2), (V) in the triclinic space group P1 (Z = 4), (VI) in the orthorhombic space group Pbca (Z = 4), (VII) in the monoclinic space group P21/n (Z = 2), and (VIII) and [Pt(PF3)8H][AsF6]·2HF in the monoclinic space group C2/c (Z = 4). -(DREWS, T.; RUSCH, D.; SEIDEL, S.; WILLEMSEN, S.; SEPPELT*, K.; Chem. Eur.