THE ISOELECTRONIC MOLECULAR-COMPLEXES TIC L(3)(NPPH(3)) AND TICL(3)(OSIPH(3))

TiCl3(NPPh(3)) and TiCl3(OSiPh(3)) have been prepared from titanium te trachloride and Me(3)SiNPPh(3) and HOSiPh(3), respectively. Both compl exes were characterized by IR spectroscopy and by crystal structure de terminations. TiCl3 (NPPh(3)): Space group R $$($) over bar 3, Z = 6, structure analysis with 959 observed unique reflections, R = 0.039. La ttice dimensions at -68 degrees C: a = b = 1370.5(7), c = 1845.9(9) pm . TiCl3(OSiPh(3)): Space group P2(1)/c, Z = 8, structure analysis with 4549 observed unique reflections, R = 0.049. Lattice dimensions at 19 degrees C: a = 2127.7(2), b = 947.2(1), c = 2136.8(1) pm, beta = 105. 081(5)degrees. Both complexes form monomeric molecules in which the ti tanium atom is tetrahedrally coordinated by three chlorine atoms, the nitrogen atom of the phosphorone iminato ligand and the oxygen atom of the silyloxy group, respectively. The bond lengths TiN of 171.9(4) pm and TiO of 171.0(3) (in average) correspond to double bonds.