O,O’-Bis(α-naphthyl, β-naphthyl and 2,3,5-trimethylphenyl) Dithiophosphate complexes of Iron (III), (II) and Iron adducts corresponding to [(RO)2PS2]3M, [(RO)2PS2]2M, and {(RO)2PS2}2Fe(Et3N)2 respectively, Where R = (α-naphthyl, β-naphthyl and 2,3,5-trimethylphenyl) and M = Iron (III), and Iron (II) have been synthesized by the reaction of sodium salts of O,O’ α-naphthyl, β-naphthyl and 2,3,5-trimethylphenyl dithiophosphate with FeCl3 and FeCl2 in equimolar ratio 3:1 and 2:1 by refluxing intoulene results in the formation of the above complexes. The adducts were prepared by the reactions of [(RO)2PS2]2Fe and donor ligands (triethylamine) in 1:2 molar stiochiometry in THF under refluxing condition for 4-5 hours. These complexes have been characterized by elemental analysis, C, H, S, N, Fe and have been further characterized by some IR and NMR (1H, 31P and 13C) spectroscopic studies which indicates bidentate linkages of dithiophosphate moieties leading to octahedral and square planar geometry around the Iron (Fe) atom.