Two new oxorhenium(V) and two new arylimidorhenium(V) complexes of the Schiff base ligands 2-hydroxy-benzaldehyde-((1R,2S)- 1-amino-2-indanol)imine (1) (H2L1) and 3-(1-adamantyl)-2-hydroxy-5-methylbenzaldehyde-((1R,2S)-1-amino-2-indanol)imine (2) (H2L2) have been prepared from the reaction of the precursor Re(O)-(PPh3)(2)Cl-3, Re(NC6H5)(PPh3)(2)Cl-3, or Re(NC6H4OCH3)(PPh3)(2)Cl-3 and the free ligands H2L1,2. The complexes Re(O)(HL1)(L-1) (3), Re(O)(HL2)(L-2) (4), Re((NCH5)-H-6)(HL1)(L-1) (5), and Re(NC(6)H(4)OCH3)(HL1)(L-1) (6) have been isolated and fully characterized by IR, H-1 NMR, circular dichroism, LRMS-FAB, and elemental analysis. All the complexes have a chiral center at rhenium. A single enantiomer is obtained in all cases. Suitable crystals of 3 and 5 were used in X-ray structural determinations. Crystal data: (3) C32H2-7N205Re-CH2CI2, orthorhombic, P2(1)2-(1)2(1), a = 9.5599(16) Angstrom, b = 9.9579(16) Angstrom, c = 31.712(5) Angstrom, V = 3018.9(9) Angstrom (3), T = 100(2) K, Z = 4. (5) C40H38N3O5Re, monoclinic, P2(1), a = 9.286(3) Angstrom, b = 18.759(6) Angstrom, c = 9.957(3) Angstrom, beta = 102.817(6)degrees, V = 1691.3(10) Angstrom (3), T = 100(2) K, Z = 2. The major characteristic of these complexes is the presence of two coordination modes for the Schiff base ligands on rhenium, a tridentate ligand (noted L1,2) and another bidentate ligand (noted HL1,2), In the latter, the -OH group of the indanol is free and tilts away from the coordination sphere. X-ray structural analyses in conjunction with circular dichroism were used to assign the absolute configuration at rhenium (C). Cyclic voltammetry, UV-vis, and circular dichroism data are presented and discussed. The complexes were found to be highly stable and to resist reduction even when treated with organic phosphanes.