Reaktionen von Oxo-Rhenium- und Diazenido-Rhenium-Komplexen mit funktionalisierten Hydrazinen. Kristall- und Molekülstrukturen von [Re(HNNC(S)Ph)(HNNHC(S)Ph)2]I · .OPPh3 · MeOH, ReO(HNNC(S)Ph)(HNNHC(S)Ph), ReCl2(PPh3)2(NNC(O)Ph)(H2NNHC(S)Ph) und ReCl2(PPh

The reaction of thiobenzoylhydrazine with ReO2I(PPh3)2 and Re2O3(S2CNEt2)4 yields [Re(HNNC(S)Ph)(HNNHC(S)Ph)2]I · OPPh3 · MeOH (1), ReO(HNNC(S)PhXHNNHC(S)Ph) (2) and Re(HNNC(S)Ph)2(S2CNEt2) (3). Re(NNC(S)OMe)(S2CNEt2)2 (4) is obtained from O-methylthiocarbazate and Re2O3(S2CNEt2)4· ReCl2(PPh3)2(NNC(O)Ph) reacts with functionalized hydrazines H2NNHR (R = C(S)Ph, C(S)OMe, C(O)SMe, C(S)SMe) to the diazenidohydrazino complexes ReCl2(PPh3)2(NNC(O)Ph)(H2NNHR) (5-8). The structures of 1, 2, 5 and 6 have been determined. 1: monoclinic, space group Cc, a = 1892.1(2), b = 1227.3(1), c = 1858.4(2) pm, β = 98.34(1)°, Ζ = 4, 4544 reflections, R = 0.034; 2: monoclinic, space group P21, a = 938.6(2), b = 637.0(1), c = 1356.0(3) pm, β = 98.96(3)°, Ζ = 2, 1905 reflections, R = 0.026; 5: triclinic, space group P1̄, a = 1236.4(2), b = 1414.8(2), c = 1780.8(3) pm, α = 111.02(2)°, β = 98.19(2)°, γ = 108.29(1)°, Ζ = 2, 4576 reflections, R = 0.067; 6: triclinic, space group P1̄̄, a = 1185.9(2), b = 1195.8(2), c = 1625.4(3) pm, a = 96.36(3)°, β = 99.54(3)°, γ = 103.93(3)°, Ζ = 2, 8006 reflections, R = 0.032. 1 and 2 contain N,S-chelating HNNR and HNNHR ligands. The ligand structures can be considered as intermediate between hydrazido(2—) or (1—) and diazene or protonated diazene type structures. In 5-8 the hydrazine derived ligands are monodentate N-coordinated.