Synthesis and spectroscopic characterization of some transition metal complexes of a new hexadentate N2S2O2 Schiff base ligand

A novel interesting hexadentate dibasic N2S2O2 donor Schiff base ligand, H4dcsalpte, was synthesized by the condensation of 3-formylsalicylic acid and 1,2-di(o-aminophenylthio)ethane and characterized. The reactions of the ligand with different metal(II/III)salts under varied reaction conditions afforded a series of metal complexes. The ligand, H4dcsalpte, behaves either as a dibasic or neutral hexadentate one, depending on the reaction conditions. Structural investigations on the ligand and their complexes have been made based on elemental analyses, molar conductance values, magnetic moment values, cryomagnetic and spectral (UV-vis, IR, 1H NMR, and Mössbauer) data. Based on magnetic susceptibility, Mössbauer and electronic spectral data the iron(III) complex [FeIII(H2dcsalpte)]ClO4 (8), isolated in the present investigation, it is inferred that the spin states 5/2 and 1/2 are in equilibrium. Similarly a tri-iron(III) complex [FeIII3(H2dcsalpte)(H3dcsalpte)Cl3]Cl3 (7), isolated in this study, has been inferred to contain two iron(III) sites in tetrahedral environment and one in the octahedral environment. The aerial oxidation of an equimolar mixture of H4dcsalpte and Co(CH3COO)2·4H2O in ethanol under reflux gave two products, [Co(H2dcsalpte)]CH3COO (10) and [(Hbtcsaldm)Co(Hbvcsaldm)] (11), a cobalt(III) complex bound to two dissimilar tridentate NSO donor ligands formed as a result of the oxidative cleavage of the CS bond. In the complex 11, Hbtcsaldm stands for the dianion of the tridentate Schiff base ligand N-(2′-benzenethiol)-3-carboxysalicylaldimine and Hbvcsaldm stands for the mono anion of the tridentate Schiff base ligand N-(benzene-2′-S-vinyl)-3-carboxysalicylaldimine, both being formed as a result of the oxidative cleavage of H4dcsalpte.