Synthesis and characterization of UO2VI, ZrOIV and VOIV complexes with Schiff base macrocyclic tetradentate ligand and their derivatives with chloroacetic acid

A series of complexes of the type [M(L)(NO3)(2)]center dot mH(2)O and [VO(L)(SO4]center dot 2H(2)O, where L is a Schiff base "2,3,5,6,10,11,13,14-octaaza-1,7,9,15-tetramethyl-1,6,9,14-cyclohexadecatetraene-4,12-dithione" derived from thiocarbobydrazide and acetylacetone have been synthesized. Reaction of these complexes with monochloroacetic acid yielded another series of complexes of the type [M(L')(NO3)(2)]center dot mH(2)O and [VO(L')(SO4)]center dot 2H(2)O, where L' is another Schiff base "4-oxo-2,3,4,5-tetrahydrothiazolo[2,3-b]-2',3',5',6',10',11',13',14'-octaaza-1',7',9',15'-tetramethyl-1',4',6',9',14'-cyclohexadecapentaene-12'-thione" obtained after cyclization with chloroacetic acid, where M = UO2VI and ZrOIV; m = 2 and 3. All the complexes are characterized on the basis of elemental analysis, thermal analysis, molar conductivity, magnetic moment, electronic, infrared, H-1 NMR and ESR spectral studies. The results indicate that the VOIV ion is penta coordinated yielding paramagnetic complexes where as UO2VI, ZrOIV ions are hexa coordinated yielding diamagnetic complexes of above stoichiometry.