Collect. Czech. Chem. Commun. 1993, 58, 1569-1590

Preparation, Spectroscopic, Magnetic, Conductometric and Polarographic Characterization of Cobalt(II)-1-phenyl-4,6-dimethylpyrimidine-2-thione Complexes

Marco Borsari, Gianantonio Battistuzzi and Raffaele Battistuzzi

Department of Chemistry, University of Modena, 41100 Modena, Italy


The following coordination compounds of cobalt(II) with 1-phenyl-4,6-dimethylpyrimidine-2-thione: CoLX2 . n H2O ( X = Cl-, n = 1; X = Br-, n = 2; X =SCN-, n = 0; X = NO3-, n = 4), Co2L3Cl4 . H2O, CoL2X2 (X = Br-, I-, SCN-, NO3-), CoL2X2 . n H2O . p Me2CO (X = I-, ClO4-, n = p = 2; X = NO3-, n = 1, p = 0), CoL3(ClO4)2 . 0.5 Me2CO, Co2L5(NO3)4 and Co2L7X4 (X = Cl-, Br-, I-) have been isolated and characterized by chemical analyses, visible and IR spectra, paramagnetic susceptibility, conductivity and polarographic measurements. Solid phase IR spectra suggest that the heterocyclic ligand is almost always bonded through non-substituted ring nitrogen and exocyclic sulfur atoms. The solid compounds with the exception of the [CoL(SCN)2]2, [CoL2(H2O)2][CoCl4] and [CoL3][CoCl4] . H2O have originally a distorted octahedral geometry. By grinding the solid [CoL2(SCN)2], Co2L7Cl4 and all the bromide complexes the cobalt(II) coordination undergo octahedral (T> tetrahedral geometry change. Spectral evidences and polarographic results in DMF solution have shown that for these and [CoL(SCN)2]2, [CoL2(H2O)2][CoCl4] and [CoL3][CoCl4] . H2O complexes, the solvolysis gives rise to equilibria between tetrahedral anionic [CoX4]2- (X = SCN-, Cl-), [CoX3(DMF)]- (X = SCN-, Cl-, Br-) and some possible [Co(DMF)6]2+, [CoX(DMF)5]+, [CoXL(DMF)4]+, [CoL(DMF)5]2+ (L = N-monodentate ligand) cationic octahedral species. Polarographic data for perchlorate complexes and for [Co(DMF)6](ClO4)2-L system at increasing ligand concentration have shown that in DMF solution the solved ions [Co(DMF)6]2+ are the prevailing species and that the thiopyrimidine-containing species [CoL(DMF)5]2+ (β = 3.78 . 105) and [CoL2(DMF)4]2+ (β =9.59 . 107) can be formed only in presence of large excess of the free ligand.