Synthesis and structure of [(Me2PhP)3Cl2ReN]2NbCl4 and [Re3N3Cl5(PMe2Ph)6][NbCl6]

The reaction of ReNCl2(PMe2Ph)(3) with NbCl5 in toluene yields the trinuclear complexes [(Me2PhP)(3)Cl2ReN](2)NbCl4 (1) and [Re3N3Cl5(PMe2Ph)(6)] [NbCl6] (2). L forms triclinic crystals with the composition 1. 2C(7)H(8) (P (1) over bar, a=1074.5(1), b=1289.1(2), c=1299.3(2)pm, alpha =85.25(2)degrees, beta =81.04(2)degrees, gamma = 86.02(1)degrees, Z = 1). In the centrosymmetric compound 1 two complexes ReNCl2(PMe2Ph)(3) coordinate with their nitrido ligands a square planar, central unit NbCl4 to form an almost linear arrangement Re equivalent toN-Nb-N equivalent to Re. The length of the Re-N triple bonds is 172,2 pm, and the Nb-N distances of 216.0 pm correspond to coordinative single bonds. 2 forms orthorhombic crystals with the space group P2(1)2(1)2(1) and a=1286.0(1), b=2109.2(4), c=2436.2(3)pm, Z = 4. The three Re atoms are located at the corners of a tri angle. They are connected by two asymmetric nitrido bridges and two asymmetric chloro bridges. The weakly bent nitrido bridges (Re-N-Re = 152 degrees and 157 degrees) are characterized by Re-N distances of 169 und 207pm as well as 171 and 207 pm. Rel, in addition, binds a terminal nitrido ligand with Re1-N1 = 166 pm.