Novel rhenium(V) complexes were isolated from reactions of [NBu(4)][ReOCl(4)] with the potentially pentadentate Schiff base PhP{C(6)H(4)-2-(HC=N(C(6)H(4)-2-OH))}(2), H(2)L(1), and the corresponding amine PhP{C(6)H(4)-2-(CH(2)-NH(C(6)H(4)-2-OH))}(2), H(4)L(2). 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 {Re(V)O}(3+) core or stabilizes a {Re(V)Cl}(4+) center by the formation of an imido-type ligand system.