SYNTHESIS AND STRUCTURE OF [RE(NH)CL-2(PME2PH)(3)][TACL6] AND [(ME2PHP)(3)CL3RE-N](2)VOCL2

The products of the reaction of ReNCl2(PMe2Ph)(3) with TaCl5 are depen dent on the solvent. In CH2Cl2 the solvent protonates the nitrido liga nd to yield [Re(NH)Cl-2(PMe2Ph)(3)][TaCl6] as air-stable, reddish brow n needles with the space group P2(1)/n and a = 1213.8(3), b = 1358.0(2 ), c = 2165.9(4) pm, beta = 92.88(1)degrees, Z = 4. The Re atom of the cation exhibits on octahedral coordination with the phosphine ligands in meridional arrangement. The imido ligand is in trans-position to a Cl atom with a distance Re-N = 170.4(4) pm. When the reaction is carr ied out in toluene the dinuclear nitrido complex [Re(NTaCl5)Cl-2(PMe2P h)(3)] is obtained instead. The reaction of ReNCl2(PMe2Ph)(3) with VCl 3(THF)(3) in toluene affords the threenuclear complex [Re2N2Cl4(PMe2Ph )(5)]VCl3, which upon crystallization at air gives air-stable, reddish -brown crystals of [(Me2PhP)(3)Cl2ReN](2)VOCl2. They crystallize in th e monoclinic space group P2(1) with a = 1519.2(5), b = 1257.1(1), c = 1564.3(6) pm, beta = 102.86(2)degrees, and Z = 2. The threenuclear com plex shows an almost linear arrangement R=N-V-N=Re with distances Re-N 171(2) pm and V-N of 209(2) pm.