Tricarbonylrhenium(I) Complexes with Thiosemicarbazone Derivatives of 2-Acetylpyridine and 2-Pyridine Formamide Showing Two Unusual Coordination Modes of Tridentate Thiosemicarbazone Ligands

[NEt(4)](2)[Re(CO)(3)Br(3)] reacts with 2-acetylpyridine phenylthiosemicarbazone (HL(1)) and 2-pyridine formamide thiosemicarbazone (HL(2)) under formation of air-stable, neutral rhenium(I) complexes of the compositions [Re(CO)(3)(L(1)-N,N,S)] and [Re(CO)(3)Br(HL(2)-N,N)]. Spectroscopic studies and X-ray crystallography show that the potentially tridentate thiosemicarbazones adopt unusual coordination modes. Whereas HL(1) deprotonates and binds to the metal in a nonplanar fashion, HL(2) acts as neutral N,N donor ligand. The bond lengths inside the chelate rings are almost uninfluenced by the overall bonding situation.