The reactions of equimolar amounts of trans-[ReOC13(PPh3)2] or trans-[Re(NPh)(PPh3)2Cl3] with a Schiff base formed by condensation of 2-hydroxy-4-methoxybenzaldehyde and ethanolamine (H2L) result in the formation of cis-[ReO(HL)PPh3Cl2] (1a) and trans-[Re(NPh)(HL)(PPh3)Cl2] (2b), respectively, in good yields. 1a and 2b have been characterized by a range of spectroscopic and analytical techniques. The X-ray crystal structures of 1a and 2b reveal that 1a is an octahedral cis-Cl,Cl oxorhenium(V) complex, while 2b is a trans-Cl,Cl phenylimidorhenium(V) complex. The complexes are weakly emissive at room temperature with quantum yields of 10-4. Density functional theory calculations of the electronic properties of the complexes were performed and are in agreement with the experimental results. The complexes display quasi-reversible Re(V)/Re(VI) redox couples in acetonitrile. There is reasonable agreement between the experimental and calculated redox potentials of 1a and 2b. © 2015 Taylor & Francis.