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

Abstract

[TiCl 4(MeCN)] 2 ( 1) is obtained from a gas phase reaction of TiCl 4 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 2 h . The Ti atoms are connected with symmetrical chloro bridges, and the octahedral coordination is completed by one acetonitrile ligand coordinated to each Ti atom. [TiCl 4(MeCN)] 2 reacts with ReNCl 2(PMe 2Ph) 3 in CH 2Cl 2 to form the dinuclear complex (Me 2PhP) 3(MeCN)ClReNTiCl 5 ( 2). It crystallizes as 2·CH 2Cl 2 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, 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 ReNCl 2(PMe 2Ph) 3 in toluene, the trinuclear complex [(Me 2PhP) 3Cl 2ReN] 2TiCl 4 ( 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.