Novel rhenium(V) complexes were isolated from reactions of [NBu4][ReOCl4] with the potentially pentadentate Schiff base PhP{C6H4-2-(HC=N(C6H4-2-OH))}2, H2L1, and the corresponding amine PhP{C6H4-2-(CH2-NH(C6H4-2-OH))}(2), H4L2. While the Schiff base undergoes partial hydrolytic decomposition and a redox reaction, the amine remains intact and acts as a pentadentate ligand, which encapsulates the metal atom of the {(ReO)-O-V}(3+) core or stabilizes a {(ReCl)-Cl-V}(4+) center by the formation of an imido-type ligand system.