The complexes of [Pt(L_n)₂] and [M(L_n)₂(OH₂)₂]Cl (M = Rh(III) and Ir(III)), where L_n = monobasic bidentate 5-(4-derivatives phenylazo)-2-thioxo-4-thiazolidinone (HL_n) have been prepared and characterized by elemental analyses, conductivity measurements, magnetic susceptibility measurements and spectroscopic (IR, Uv.-Vis. and ¹H NMR) studies. The X-ray diffraction (XRD) pattern of the ligand (HL₂) is polycrystalline nature. The molecular, electronic structures and quantum chemical parameters of the ligands (HL_n) were studied. Molecular docking was used to predict the binding between ligands (HL_n) and the receptor of breast cancer 3HB5 oxidoreductase. The Rh(III) and Ir(III) complexes are six-coordinate distorted octahedral, whereas Pt(II) is four coordinated. The ligand coordinates through the azo dye nitrogen atom and enolic oxygen atom after deprotonation. The molar conductivities show that all the complexes of Pt(II) are non-electrolytes while Rh(III) and Ir(III) complexes are electrolytic nature. The ligands field parameters were calculated using various energy level diagrams.