AbstractThe synthesis of a novel benziloxime ligand, 4,4′‐dibromobenzilmonoxime (DBBOH) (1) and its complexes [Fe(DBBO)3] (2) and Na[Ni(DBBO)3] (3) are described. The ligand (DBBOH) was prepared in MeOH from the reaction of 4,4′‐dibromobenzil with hydroxylamine hydrochloride in the presence of sodium acetate.Reaction of sodium salt of 4, 4′‐dibromobenzilmonoxime (DBBONa) in MeOH with Fe(NO3)3.9H2O and Ni(NO3)2.6H2O yielded [Fe(DBBO)3](2) as yellow and Na[Ni(DBBO)3] (3) as brown precipitates respectively.The ligand, 4, 4′‐dibromobenzilmonoxime (DBBOH) (1) and its complexes [Fe(DBBO)3](2) and Na[Ni(DBBO)3] (3) were characterized by elemental analysis,1H‐NMR and13C‐NMR, IR, and electronic spectral studies.The analysis of IR,1H‐ and13C‐NMR spectral data of Fe(III) and Ni(II) complexes suggest that 4,4′‐dibromobenzilmonoximate is bonded to iron(III) and nickel(II) ions through the oxygen atom of the carbonyl, and the nitrogen atom of the imine groups. The electronic spectral data of the complexes in CHCl3 are in good agreement with the octahedral coordination of Fe(III) and Ni(II) ions. The ligand field parameters for these complexes, i.e. splitting energy and Racah parameter were calculated to be 21560 cm−1and 707 cm−1for [Fe(DBBO)3] (2), 13440 cm−1and 610 cm−