Simple Preparations of Pd6Cl12, Pt6Cl12, and Qn[Pt2Cl8+n], n = 1, 2 (Q = TBA+, PPN+) and Structural Characterization of [TBA][Pt2Cl9] and [PPN]2[Pt2Cl10]•C7H8

The hexanuclear Pd6Cl12, i.e., the crystal phase classified as β-PdCl2, was obtained by reacting [TBA]2[Pd2Cl6] with AlCl3 (or FeCl3) in CH2Cl2. The action of AlCl3 on PtCl4^2-, followed by digestion of the resulting solid in 1,2-C2H4Cl2 (DCE), CHCl3, or benzene, produced Pt6Cl12•DCE, Pt6Cl12•CHCl3, or Pt6 Cl12•C6H6, respectively. Treating [TBA]2- [PtCl6] with a slight excess of AlCl3 afforded [TBA][Pt2Cl9], whose anion was established crystallographically to be constituted by two “PtCl6” octahedra sharing a face. Dehydration of H2PtCl6•nH2O with SOCl2 gave an amorphous compound closely analyzing as PtCl4, reactive with [Q]Cl in SOCl2 to yield [Q][Pt2Cl9] or [Q]2[Pt2Cl10], depending on the [Q]Cl/Pt molar ratio (Q ) TBA+, PPN+). A single-crystal X-ray diffraction study has shown [PPN]2[Pt2Cl10]•C7H8 to contain dinuclear anions formed by two edge-sharing PtCl6 octahedra.