T. Rubenstahl et al., PHOSPHORANEIMINATO COMPLEXES OF VANADIUM - THE CRYSTAL-STRUCTURE OF [V3CL6(NPME(3))(5)(-)]CENTER-DOT-6 CH3CN()](2)[V4O4CL8(NPME(3))(2)(2), Zeitschrift fur anorganische und allgemeine Chemie, 621(7), 1995, pp. 1218-1222
Citations number
15
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
Zeitschrift fur anorganische und allgemeine Chemie
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.