We have synthesized a series of novel octahedral Rh(III) salen-type complexes when the salen ligand is unsymmetrically bound to the Rh(III) dichloride center. This mode of bonding left one intact phenol group coordination to the rhodium center and has never before been observed in salen - metal chemistry. These remarkably stable complexes possess unique coordination geometry and represent the first time that Rh(III) salen complexes have been successfully isolated from the direct combination of RhCl3. 3H(2)O and the salen ligand in the absence of a nucleophilic base. The (salen)Rh(III) dichloride complex can be converted to the analogous monochloride complex by reaction with metal carbonate salts.