PHOSPHORANE IMINATO COMPLEXES OF SULFUR - SYNTHESIS AND CRYSTAL-STRUCTURES OF [SO(CL)(NPPH(3))], [SO2(CL)(NPPH(3))], AND [SCL(NPPH(3))(2)]CL

The title compounds have been prepared by the reaction of Me(3)SiNPPh( 3) with SOCl2, SO2Cl2, and SCl2, respectively. They form colourless, m oisture sensitive crystals, which were characterized by IR spectroscop y and by crystal structure determinations. [SO(Cl)(NPPh(3))]: Space gr oup P2(1)/n, Z = 4, structure determination with 2434 observed unique reflections, R = 0.047. Lattice dimensions at 19 degrees C: a = 1304.8 , b = 996.5, c = 1339.5 pm, beta = 93.75 degrees. The compound forms m onomeric molecules with a remarkably long S-Cl bond of 234.2 pm and di stances SN and PN of 154.6 and 161.6 pm, respectively, which agree wit h double bonds. [SO2(Cl)(NPPh(3),)]: Space group P2(1)/n, Z = 4, struc ture solution with 2872 observed, unique reflections, R = 0.047. Latti ce dimensions at 20 degrees C: a = 956.9, b = 1909, c = 1002.0 pm, bet a = 106.06 degrees. The compound forms monomeric molecules with distan ces S-Cl of 207.1 pm, SN of 154.5 pm, and PN of 161.6 pm. [SCl(NPPh(3) )(2)]Cl: Space group P2(1)/c, Z = 4, structure solution with 5224 obse rved, unique reflections, R = 0.042. Lattice dimensions at 20 degrees C: a = 1108.6, b = 1603.8, c = 1840.5 pm, beta = 99.98 degrees. The co mpound forms ions [SCl(NPPh(3))(2)](+) and Cl-. In the cation the sulf ur atom is phi-tetrahedrally coordinated with a long S-Cl distance of 248.5 pm and SN bond lengths of 154.5 and 156.0 pm.