SYNTHESES AND CRYSTAL-STRUCTURES OF THE PHOSPHORANE IMINATO COMPLEXES [MCL(2)(NPPH(3))](2) WITH M=AL AND GA, [SBCL2(NPME(3))(DMF)](2), AND OF THE PHOSPHORANE IMINE COMPLEX [PH(3)PNH-CENTER-DOT-BF3]CENTER-DOT-THF

The phosphorane iminato complexes [MCl(2)(NPPh(3))](2) with M = Al and Ga and [SbCl2(NPMe(5))(DMF)](2) are formed as colourless crystals by reactions of the anhydrous trichlorides MCl(3) (M = Al, Ga, Sb) with the corresponding silylated phosphorane imines Me(3)SiNPR(3) in acetonitrile and in dimethyl formamide, respectively. The phosphorane imine derivative [Ph(3)PNH . BF3] . THF is formed from Me(3)SiNPPh(3) and boron trifluoride etherate in boiling tetrahydrofuran. The compounds are characterized by their i.r. spectra and by crystal structure analyses. [AlCl2(NPPh(3))](2): Space group P $($) over bar$$ 1, Z = 1, structure solution with 1585 observed unique reflections, R = 0.061. Lattice dimensions at -70 degrees C: a = 917.6, b = 1053.5, c = 1145.2 pm, alpha = 111.72 degrees, beta = 100.80 degrees, gamma = 109.95 degrees. [GaCl2(NPPh(3))](2): Space group P $($) over bar$$ 1, Z = 1, structure solution with 2586 observed unique reflections, R = 0.066. Lattice dimensions at -70 degrees C: a = 917.5, b = 1058.3, c = 1 153.7 pm, alpha = 105.52 degrees, beta = 107.75 degrees, gamma = 109.88 degrees. In both compounds the metal atoms are linked to planar M(2)N(2) four-membered rings via the N-atoms of the phosphorane iminato groups. [SbCl2(NPMe(3))(DMF)](2): Space group P2(1)/n, Z = 4, structure solution with 3805 observed unique reflections, R = 0.038. Lattice dimensions at -70 degrees C: a = 1913.0, b = 726.8, c = 2040.7 pm, beta = 113.62 degrees. The unit cell contains two symmetry independent dimeric molecules, in which the antimony atoms are centrosymmetricly mu(2) linked via the N-atoms of the phosphorane iminato groups. Along with the oxygen atom of the dimethyl formamide molecule the Sb atoms achieve a psi-octahedral environment. [Ph(3)PNH . BF3] . THF: Space group C2/c, Z = 8, structure solution with 2048 observed unique reflections, R = 0.058. Lattice dimensions at -70 degrees C: a = 2460.4, b = 869.2, c = 1978.0 pm, beta = 116.35 degrees.