Structural, spectral, DFT, pH-metric and biological studies on Cr(III), Mn(II) and Fe(III) complexes of dithione heterocyclic thiosemicarbazide ligand

Cr(III), Mn(II) and Fe(III) complexes derived from the quadruple potential dithione heterocyclic thiosemicarbazide ligand (H2PET) have been prepared and characterized by conventional techniques. The isolated complexes were assigned the formulae, [Cr(HPET)(H2O)(2)Cl-2]center dot 3H(2)O, [Mn(HPET)(H2O)Cl](2) and [Fe(HPET)(H2O)(2)Cl-2]center dot H2O, respectively. IR data revealed that the ligand behaves as monobasic bidentate through (C=N)(py) and (C-S) groups in both Cr(III) and Fe(III) complexes. In the binuclear Mn(II) complex, H2PET acts as NSNS monobasic tetradente via (C=N)(py), (C-S), (C=S) and the new azomethine, (N=C)* groups. An octahedral geometry for all complexes was proposed. The bond lengths, bond angles, HOMO, LUMO and dipole moment have been calculated by DFF using materials studio program to confirm the geometry of H2PET and its metal complexes. The ligand association constant and the stability constants of its complexes in addition to the thermodynamic parameters were calculated from pH metrically at 298, 308 and 318 degrees K in 50% dioxane-water mixture, respectively. Also, the kinetic and thermodynamic parameters for the different thermal degradation steps of the complexes were determined by Coats-Redfern and Horowitz-Metzger methods. Moreover, the anti-oxidant (using ABTS and DPPH methods), anti-hemolytic, and cytotoxic activities of the compounds have been tested. (C) 2012 Elsevier B.V. All rights reserved.