Synthesis and structure of [(Me2PhP)(3)Cl2ReN](2)ReCl4, [(Me2PhP)(3)Cl2ReN](2)ReCl4 center dot 2 SbCl3 and [Re(NH)Cl-2(PMe2Ph)(3)][SbCl6]

The reaction of ReNCl2(PMePh)(3) with SbCl5 in toluene yields the trinuclea r complex [(Me2PhP)(3)Cl2Re=N](2-) ReCl4 . 2SbCl(3) (1.2SbCl(3)). It forms triclinic crystals with the composition 1.2SbCl(3), as well as monoclinic c rystals 1.2SbCl(3). 4C7H(8). The monoclinic crystals with the space group P 2(1)/c, and a = 1212.3(2), b = 2098.5(4), c = 1827.7(3) pm, beta = 95.51(1) degrees, Z = 2, have been used for a crystal structure determination. In th e centrosymmetric complex 1 two complexes ReNCl2(PMe2Ph)(3) coordinate with their nitrido ligands a square planar, central unit ReCl4. The SbCl3 molec ules are coordinated by chlorine bridges to Cl atoms of 1, and, in addition , connect the complexes 1 with each other. The SbCl3 free compound 1 is obt ained in good yield by the reaction of ReNCl2(PMePh)(3) with ReCl4(NCEt)(2) . It crystallizes in the triclinic space group P (1) over bar with a = 1037 .7(3), b = 1153.0(2), c = 1393.8(3) pm, alpha= 72.31(2)degrees, beta= 74.06 (2)degrees, gamma = 67.94(2)degrees, and Z = 1. The bond lengths of the Re- N triple bonds are 172 pm in 1 and 170 pm in 1.2SbCl(3). By the reaction of ReNCl2(PMePh)(3) with SbCl5 in CH2Cl2 the solvent is dec omposed forming HCl which protonates the nitrido ligand to afford the imido complex [Re(NH)Cl-2(PMe2Ph)(3)] [SbCl6] (2) crystallizing in the monoclini c space group P2(1)/n with a = 1221.4(2), b = 1358.6(2), c = 2177.3(1) pm, beta = 92,72(1)degrees and Z = 4. The Re-N distance in the almost linear un it Re=N-H is 169,1 pm.