Abstract
The reactions of N-(O-hydoxyphenyl)-N'-phenylthiourea (L) derived from with Cu+, Cu2+, Co2+ and Co3+ chloride and/or iodide afford new metal complexes. The isolated complexes were synthesized by two different techniques (chemical and tribochemical methods). Two complexes were synthesized by the direct chemical reactions of N-(O-hydoxyphenyl)-N'-phenylthiourea (L) with MCl2·XH2O (M = Co2+ and Cu2+; X = 6 in case of Co2+ and X = 2 in case of Cu2+) in absolute EtOH. The general formulae of the two complexes derived by the chemical method are [Cu(L)2(EtOH)2]Cl2 and [Co(L)2Cl2]Cl. These complexes were used to synthesize another two complexes using tribochemical reaction by grinding the previous chloride complexes with excess KI in agate mortar in the solid state. The isolated complexes have the general formulae, [Cu(L)I·H2O]·1/2H2O and [Co(L)I3(Et- OH)]·3EtOH. The results indicate the substitution of the chloride by iodide ions during grinding and extraction of the complexes by solvents. The IR spectra of the complexes suggest that L acts in a bidentate manner towards the metal ions. Moreover, the results of electronic spectra and magnetic measurements for the chloride complexes suggest distorted-octahedral structure for Cu2+ and low-spin octahedral structures around the CoII and Cu2+ ions, respectively. On the other hand the data suggest that the iodide complexes have square-planer and low-spin for the Cu+ and Co3+ ions, respectively. The results of mass spectra confirm the formulae proposed for the isolated complexes. The mechanisms of reduction of CuII and oxidation of CoII for the metal complexes were elucidated.
Highlights
Thiourea is the analogue compound to urea and has a considerably wide range of applications
Preparation of Cu2+ and Co2+ Complexes by Chemical Method Two complexes derived from Cu2+ and Co2+ ions with the general formulae, [Cu(L)2(EtOH2)]Cl2 and [Co(L)2Cl2]Cl, were synthesized by the direct reaction of CuCl2·2H2O (1.7 g, 0.01 mol) and/or CoCl2·6H2O (2.8 g, 0.01 mol) dissolved in EtOH (50 ml) with N-(O-hydoxyphenyl)-N'-phenylthiourea (4.8 g, 0.01 mol) dissolved in absolute EtOH (25 ml)
The electrolytic nature of these complexes [16], except the two iodide complexes of the general formulae, [Cu(L)I·H2O]·1/2H2O and [Co(L)I3·EtOH]·3EtOH are non-conducting in DMSO
Summary
Thiourea is the analogue compound to urea and has a considerably wide range of applications. Thiourea derivatives are selective analytical reagents, especially for the determination of transition metal in complexes [2]. The biological activity of thiourea complexes has been successfully screened for various biological actions. The complexing capacity of thiourea derivatives has been reported in several papers [9] [10]. The metal complexes of thiourea are neutral and their colors vary with the nature of the metal ions. These chelating agents have been remarkable ones for analytical chemistry [11]. Thiourea coordinates to metal ions as neutral ligands, monoanions and dianions [12] [13].
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