Syntheses and structures of di- and trinuclear heterometallic complexes with nitrido bridges between rhenium and titanium

[TiCl4(MeCN)](2) (1) is obtained from a gas phase reaction of TiCl4 and MeCN. It crystallizes in the orthorhombic space group Cmca with the cell constants a = 961.8(2), b = 984.0(5), c = 1637.0(4) pm, and Z = 4. The symmetry of the dinuclear complex is C-2h. The Ti atoms are connected with symmetrical chloro bridges, and the octahedral coordination is completed by one acetonitrile ligand coordinated to each Ti atom. [TiCl4(MeCN)](2) reacts with ReNCl2(PMe2Ph)(3) in CH2Cl2 to form the dinuclear complex (Me2PhP)(3)(MeCN)ClRe=N-TiCl5 (2). It crystallizes as 2.CH2Cl2 in the monoclinic space group P2(1)/n with the cell constants a = 982.0(2), b = 1245.3(2), c = 3088.1(5) pm, beta = 92.44(2)degrees, and Z = 4. The linear nitrido bridge (Re-N-Ti = 167.7(4)degrees) is characterized by distances Re-N = 167.6(8) pm and Ti-N = 223.9(9) pm. By using a fourfold excess of ReNCl2(PMe2Ph)(3) in toluene, the trinuclear complex [(Me2PhP)(3)Cl2ReN](2)TiCl4 (3) is obtained in form of crystals 3.2 toluene: P (1) over bar, a = 1070.4(2), b = 1283.2(5), c = 1300.0(3) pm, alpha = 85.21(2)degrees, beta = 80.57(2)degrees, gamma = 86.19(3)degrees, Z = 1. The centrosymmetric complex 3 contains a linear axis Re=N-Ti-N=Re with a Re-N distance of 168.5(9) pm and a Ti-N distance of 215.7(9) pm. (C) 2000 Elsevier Science S.A. All rights reserved.