Phosphaniminato-Komplexe des Schwefels. Synthese und Kristallstrukturen von [SO(Cl)(NPPh3)], [SO2(Cl)(NPPh3)] und [SCl(NPPh3)2]Cl

Phosphorane Iminato Complexes of Sulfur. Synthesis and Crystal Structures of SO(Cl)(NPPh₃)], SO₂(Cl)(NPPh₃)], and SCl(NPPh₃)₂]Cl The title compounds have been prepared by the reaction of Me₃SiNPPh₃ with SOCl₂, SO₂Cl₂, and SCl₂, respectively. They form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations. SO(Cl)(NPPh₃)]: Space group P2₁/n, Z = 4, structure determination with 2 434 observed unique reflections, R = 0.047. Lattice dimensions at 19°C: a = 1 304.8, b = 996.5, c = 1 339.5 pm, β = 93.75°. The compound forms monomeric molecules with a remarkably long S? Cl bond of 234.2 pm and distances SN and PN of 154.6 and 161.6 pm, respectively, which agree with double bonds. SO₂(Cl)(NPPh₃)]: Space group P2₁/n, Z = 4, structure solution with 2 872 observed, unique reflections, R = 0.047. Lattice dimensions at 20°C: a = 956.9, b = 1 909, c = 1 002.0 pm, β = 106.06°. The compound forms monomeric molecules with distances S? Cl of 207.1 pm, SN of 154.5 pm, and PN of 161.6 pm. SCl(NPPh₃)₂]Cl: Space group P2₁/c, Z = 4, structure solution with 5 224 observed, unique reflections, R = 0.042. Lattice dimensions at 20°C: a = 1 108.6, b = 1 603.8, c = 1 840.5 pm, β = 99.98°. The compound forms ions SCl(NPPh₃)₂]⁺ and Cl^?. In the cation the sulfur atom is φ-tetrahedrally coordinated with a long S? Cl distance of 248.5 pm and SN bond lengths of 154.5 and 156.0 pm.