[NEt4](2)[Re(CO)(3)Br-3] reacts with 2-acetylpyridine phenylthiosemicarbazone (HL1) and 2-pyridine formamide thiosemicarbazone (HL2) under formation of air-stable, neutral rhenium(l) complexes of the compositions [Re(CO)(3)(L-1-N,N,S)] and [Re(CO)(3)Br(HL2 -N,N)]. Spectroscopic studies and X-ray crystallography show that the potentially tridentate thiosemicarbazones adopt unusual coordination modes. Whereas HL1 deprotonates and binds to the metal in a nonplanar fashion, HL2 acts as neutral N,N donor ligand. The bond lengths inside the chelate rings are almost uninfluenced by the overall bonding situation.