Synthesis, Spectroscopic Investigations, Thermal Analysis And DFT Calculations Of Some Pentacarbonyl(Mercaptopyrimidine)Metal(0) Complexes Of Group VI B Elements

Pentacarbonyl-N-mercaptopyrimidinemetal(0) complexes of VIB metals (M: Cr, Mo, W) were formed when hexacarbonylmetal(0) complexes are treated photochemically with 4,6-dimethyl-2-mercaptopyrimidine at 10 ºC. The reported organometallic complexes were purified and isolated under an inert atmosphere. All M(CO)5L complexes were characterized in solution by FTIR-, 1H- and 13C-NMR spectroscopies. The FTIR spectroscopy results showed three absorption bands in the carbonyl region which indicates that the pentacarbonyl metal unit of the complexes has a local C4v symmetry. The 1H- and 13C-NMR spectroscopies showed that the mercaptopyrimidine ligand bonded to the metal complex through the mercaptopyrimidine-nitrogen atom symmetrically. The 13C-NMR spectroscopy results also showed a 1:4 ratio of two peaks in the CO-region, the ratio of the peaks proved the C4v symmetry of these complexes. The thermal behavior of these organometallic complexes is investigated by using DTA/TGA methods. The results of thermal analyses showed that the complexes decomposed at three different temperatures. The density functional theory (DFT) calculations were computed in B3PW91 formalism by Gaussian03W Software. The comparison of the experimental data with the theoretical values showed that the results obtained are compatible with each other. Thus, the accuracy of the experimentally given structural proposal of the obtained organometallic complex compounds was also confirmed through theoretical calculations.