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 C2h. 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 P21/n with the cell constants a=982.0(2), b=1245.3(2), c=3088.1(5) pm, β=92.44(2)°, and Z=4. The linear nitrido bridge (ReNTi=167.7(4)°) 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)3Cl2ReN]2TiCl4 (3) is obtained in form of crystals 3·2 toluene: P1̄, a=1070.4(2), b=1283.2(5), c=1300.0(3) pm, α=85.21(2)°, β=80.57(2)°, γ=86.19(3)°, 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.