Metall-Schwefelstickstoff-Verbindungen. 20. Reaktionsprodukte von PdCl2 und Pd(CN)2 mit S7NH. Darstellung und Struktur der Komplexe [Ph6P2N][Pd(S3N)(S5)] und X[Pd(S3N)(CN)2] (X = [Me4N]+, [Ph4P]+)

Metal Sulfur Nitrogen Compounds. 20. Reaction Products of PdCl₂ and Pd(CN)₂ with S₇NH. Preparation and Structure of the Complexes Ph₆P₂N]Pd(S₃N)(S₅)] and XPd(S₃N)(CN)₂] X = Me₄N]⁺, Ph₄P]⁺ With PdCl₂ and Ph₆P₂N]OH S₇NH forms the complex salt Ph₆P₂N]Pd(S₃N)(S₅)], which could be isolated in two modifications (α- and β-form). The α-form is triclinic, a = 9.347(4), b = 14.410(8), c = 15.440(11) Å, α = 76.27°(5), β = 77.06°(4), γ = 76.61α(4), Z = 2, space group P1 . The β-form is orthorhombic, a = 9.333(2), b = 17.659(4), c = 23.950(6) Å, Z = 4. The structure of the metal complex is the same in the two modifications. One S₃N^? and one S₅^2? are coordinate as chelate ligands to Pd. From S₇NH, Pd(CN)₂, and XOH X = (CH₃)₄N]⁺ and (C₆H₅)₄P]⁺ the salts XPd(S₃N)(CN)₂] were formed. The (CH₃)₄N-salt is isomorphous with the analogous Ni compound described earlier, the (C₆H₅)₄P-salt is triclinic, a = 9.372(4), b = 10.202(5), c = 13.638(6) Å, α = 86.36α(4), β = 85.66°(4), γ = 88.71°(4), Z = 2, space group P1 . One S₃N^? chelate ligand and two CN^? ions are bound to Pd. In all these complexes the coordination of Pd is nearly square planar.