Synthesis of polyfunctional ligands based 1,10-phenanthroline and investigation of their metal complexes

1,10-Phenanthroline and its derivatives are ligands chelating which have an important role insynthesis of polypyridyl metal complexes. The metal-chelating properties of the 1,10-phenantroline ligand and its derivatives have been extensively used in bioorganic researches,analytical chemistry and preparative coordination chemistry. Recently, sysnthesis andcoordinating properties of various metal complexes of some mixed aza-thioether crowns havebeen investigated. Especially, properties of selective metal catching compounds consisting ofthioether, thiourea groups have been investigated and electrochemical behaviours.In this study, we were synthesized some new type of ligands , having 1,10-phenanthroline,thiourea and crown ether groups and their metal complexes. Their structures have beeninvestigated and characterized.First of all, the derivatives of 1,10-phenanthroline and 15-isothiocyanatobenzo[15-crown-5]have been synthesized., 5-nitro-1,10-phenanthroline and then 5-nitro-6-amino-1,10-phenanthroline have been synthesized during the synthesis of derivatives of 1,10-phenanthroline. At last, 5,6-diamino-1,10-phenanthroline has been synthesized by thereduction of 5-nitro-6-amino-1,10-phenanthroline with Pd/C and hidrazin hydrate. Moreover,5-amino-1,10-phenanthroline has been synthesized by the reduction of nitro group in 5-nitro-1,10-phenanthroline.Then, after the result of addition reaction of 5-amino-1,10-phenanthroline and 5,6-diamino-1,10-phenanthroline with 15-isothiocyanatobenzo[15-crown-5] and 5,6-diamino-1,10-phenanthroline with phenyl isothiocyanate the new 6-amino-5-ylamino-anilinomethanethione[1,10]phenanthroline (1), 5,6-bis[benzo[15-crown-5]-15-ylaminothioxomethylamino][1,10]phenanthroline (2) , 6-amino-5-ylamino-benzo[15-crown-5]-15-ylaminoethanethione[1,10]phenanthroline (3) and N-[1,10-phenanthroline]-N`-{[benzo-15-crown-5] yl}thiourea(8) ligands have been synthesized. Finally, Cu(I), Cu(II), Ni(II) and Co(II) complexes of theseligands have been synthesized.All of the synthesized compounds have been investigated and characterized by elementalanalysis, UV-Vis, FTIR, 1H NMR, 13C NMR and MS spectras. Synthesized ligands andCo(II), Ni(II) and Cu(II) complexes have been studied potentiometrically, protonation andoverall formation constants have been calculated from potentiometric data using the computerprogram TITFIT.Keywords : 1,10-Phenanthroline, Crown ether, Thiourea, Macrocyclic complex