Ionische Phosphaniminato-Komplexe von Schwefel(IV) und Selen(IV ). Die Kristallstrukturen von [S(NPMe3)3]Cl · CH2Cl2, [S(N PPh3)3]S4N5 und [Se(NPMe3)3]Cl · C7H8 / Ionic Phosphorane Iminato Complexes of Sulfur(IV) and Selenium(IV). Crystal Structures of [S(NPMe3)3]Cl ·CH2Cl2, [S(NPPh3)3]S4N5 and [Se(NPMe3)3]Cl · C7H8

Abstract

[S(NPMe3)3]Cl · CH2C12 and [S(NPPh3)3]S4N5 were prepared by the reaction of Me3SiNPMe3 or Me3SiNPPh3 with sulfur dichloride and S3N2Cl2, respectively, in CH2Cl2 solutions as colourless, moisture sensitive crystals. The corresponding selenium compound was prepared from SeCl4 and Me3SiNPMe3 in acetonitrile solution; it crystallizes from toluene solutions with one mole of toluene per formula unit. All complexes have been characterized by IR spectroscopy and by crystal structure determinations. [S(NPMe3)3]Cl-CH2Cl2: Space group Pna21, Z = 8 , 3930 observed unique reflections, R = 0.033. Lattice dimensions at -120 °C: a = 1200.9(1), b = 1020.2(1), c = 1790.5(1) pm. [S(NPPh3)3]S4N5: Space group P63, Z = 2, 2586 observed unique reflections, R = 0.054. Lattice dimensions at -100 °C: a = b = 1334.7(2), c = 1652.6(2) pm. [Se(NPMe3)3]Cl · C7H8: Space group C2/c, Z = 8 , 1475 observed unique reflections, R = 0.059. Lattice dimensions at -40 °C: a = 1853.6(8), b = 1159.2(4), c = 2053.2(4) pm. β = 101.92(3)°. All compounds contain cations [E(NPR3)3]+ (E = S, Se) with pyramidal structures. Bond lengths and bond angles are in average: S-N 162.5 pm, S-N-P 120.5° (R = Me), S-N 161.8 pm, S-N-P 119.2° (R = Ph), Se-N 177.8 pm, Se-N-P 120.3°.