PHOSPHORANEIMINATO COMPLEXES OF VANADIUM - THE CRYSTAL-STRUCTURE OF [V3CL6(NPME(3))(5)(-)]CENTER-DOT-6 CH3CN()](2)[V4O4CL8(NPME(3))(2)(2)

Vanadiumtetrachloride reacts in CCl4 solution with Me(3)SiNPMe(3) to f orm the donor acceptor complex [VCl4(Me(3)SiNPMe(3))], which reacts wi th excess Me(3)SiNPMe(3) in boiling acetonitrile to form the phosphora neiminato complex [V3Cl6(NPMe(3))I]Cl-+(-). Partial hydrolysis in acet onitrile solution leads to black single crystals of [V3Cl6(NPMe(3))(5) (+)](2-) [V4O4Cl8(NPMe(3))(2)(2-)] . 6CH(3)CN, which are characterized by a crystal structure determination. Space group P2(1)/c, Z = 2, str ucture solution with 3008 observed unique reflections, R = 0.090. Latt ice dimensions at -70 degrees C: a = 1379.0, b = 1915.8, c = 2278 pm, beta = 102,79 degrees. In the complex cation the three vanadium atoms form a trigonal bipyramid with two mu(3)-NPMe(3) groups; the residual NPMe(3)(-) groups and the chlorine atoms are in terminal functions. In the anion [V4O4Cl8(NPMe(3))(2)](2-) the vanadium atoms are linked by mu(2)-O atoms to form a rectangle; in addition the two phosphoraneimin ato ligands form mu(2)-N bridges.