Rhenium (V) complexes with the following multidentate dipyridyl ligands were prepared: 2, 2'-dipyridylamine (DPA), 1, 2-bis (2-pyridyl) ethylene (DPE) and di- (2-picolyl) amine (HDIPA). Reactions of a twfold molar excess of the potentially NN donor ligand DPA with trans-[ReO (OEt) Cl₂ (PPh₃) ₂] in ethanol led to isolation of a monomer [ReOCl₂ (OEt) (DPA) ] (1). Treatments of traps-[ReOCl₃ (PPh₃) ₂] with a tenfold molar excess of DPA in ethanol at reflux yielded [ReO₂ (dpa) ₂]Cl (2), but with a twofold molar excess a dimer (μ-O) [{ReOCl₂ (dpa) }₂] (3a) was isolated. The latter reaction with (n-Bu₄N) [ReOCl₄] as starting material in ethanol at room temperature led to a dark green product, also with the formulation (μ-O) [{ReOCl₂ (dpa) }₂] (3b). Reacting equimolar quantities of (n-Bu₄N) [ReOCl₄] and HDIPA in acetone led to [ReOCI (OH₂) (DIPA) ]Cl (4) in which HDIPA acted as a monoanionic terdentate chelate. The reaction of trans-[ReOCl₃ (PPh₃) ₂] with DPE, in which DPE undergoes a metal-promoted nucleophilic attack by a water molecule, produces a complex with a general formula [ReO (DPE. OH) Cl₂] (5).