Metal exchange reactions in cadmium complexes with porphyrins of various structures |
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Authors: | D B Berezin O V Shukhto M S Reshetyan |
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Institution: | 1.Ivanovo State University of Chemical Technology,Ivanovo,Russia |
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Abstract: | The reaction kinetics of the metal exchange Cd(II)-Cu(II) and Cd(II)-Zn(II) in the cadmium complexes (CdP) with porphyrin
ligands (H2P) differing by degree of stiffness (tetraphenylporphin, N-methyltetraphenylporphin, and tetraphenyltetrabenzoporphin) in the DMSO medium, was studied using spectrophotometric method.
The rate of metal exchange reaction depends on the nature of the non-planatrity of H2P in the structure of CdP complexes, as well as on the additional screening of the reaction center MN4 by the extra-ligands and substituents. The reduction of the coordinating ability of the anion X− in the structure of the solvate-salt of incoming metal M’X2(Solv)
n−2 in a series: acetylacetonate > acetate > chloride > nitrate favors the metal exchange. In the most studied cases the reaction
of CdP proceeds along a combined associative-dissociative mechanism. The order of the metal exchange reaction is found to
be depending on temperature indicating a change in the contributions of associative and combined routes. The “pure” associative
reaction mechanism in a medium of DMSO was for the first time found for the labile complex CdTPTBP with the saddle-type nonplanar
ligand. |
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