Radiopharmaceuticals containing the "fac-{M(CO)(3)}(+)" core (M = Tc-99m, Re-186, or Re-188) have potential as diagnostic or therapeutic agents. Complexes with this core with sp(3) amine donors have received little attention. We have studied adducts formed by ENDACH(2) (HO2CCH2NHCH2CH2NHCH2CO2H) and ENACH (NH2CH2CH2NHCH2CO2H). Re(CO)(3)(ENDACH)-A (1A) and Re(CO)(3)(ENDACH)-B (1B) isomers were obtained by the reaction of ENDACH(2) with Re(CO)(5)Cl. Re(CO)(3)(ENAC) (2) was obtained by the reaction of ENACH with aqueous [Re(CO)(3)(H2O)(3)](+). From single-crystal X-ray data, the three new neutral complexes, 1A, 1B, and 2, have a six-coordinate, pseudo-octahedral Re center with facially coordinated carbonyl ligands. ENDACH(-) and ENAC(-) bind facially to Re through both amine nitrogens and one carboxyl oxygen, forming two five-membered chelate rings. The Re(CO)(3)(ENDACH) isomers have an uncoordinated, dangling -CH2CO2H group, which is an ideal coupling site for attachment to biomolecules. The isomers differ by the configuration of the NH center bearing this dangling group. The H atom of the amine (N2) is endo (near the carbonyl ligands in the basal plane) in 1A and exo (away from carbonyl ligands) in isomer 1B. Isomers reach equilibrium (1A:1B, 70:30) after 3 days at high pH. Density functional structure optimizations were performed for isolated molecules of the type Tc-I/Re-I(CO)(3)(N2O): [Re(CO)(3)(NH3)(2)(H2O)](+), [Tc(CO)(3)(NH3)(2)(H2O)](+), [Re(CO)(3)(EN)(H2O)](+) (EN, ethylenediamine), [Tc(CO)(3)(EN)(H2O)](+), and various models for 1A, 1B, and 2. The computed structures are in good agreement with the X-ray structures. The theoretical and experimental Re-N bond distances usually agree within 0.045 Angstrom. The total electronic energy values for the computed 1A and 1B models differ by 0.815 kcal mol(-1), giving an isomer ratio of 80:20, in good agreement with the 1A/1B ratio (70:30) found.