A number of Re complexes with N,N ' -bis(2-pyridylmethyl)ethylenediamine (H(2)pmen) have been made from [NH4]-[ReO4]. . [ReOCl(2)H(2)pmen)]Cl, [ReOCl(Hpmen)][ReO4], and [ReO2(H(2)pmen)] [ReO4] are related by hydrolysis/HCl substitution [ReOCl(Hpmen)] [ReO4] was structurally characterized and found to contain a water-stable amido-Re bend. Dehydrogenation of the N-donor ligand from each amine to imine with concomitant two-electron reduction of the Re center occurs readily in these systems. With suitable 3-hydroxy-4-pyrones, ternary complexes such as [(ReCl)-Cl-III(ma)(C14H14N4)][ReO4]. CH3OH, 5, were made from [NH4][ReO4], H(2)pmen . 4HCl and pyrones in one-pot syntheses. 5, a seven-coordinate Re-III complex, was structurally characterized.