5-(pyridylmethylidene)-substituted 2-thiohydantoins and their complexes with Cu-II, Ni-II, and Co-II: synthesis, electrochemical study, and adsorption on the cystamine-modified gold surfaceстатья
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Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
Аннотация:A series of Cu-II, Ni-II, and Co-II complexes with 5-(pyridylmeth ylidene)-substituted 2-thiohydantoins (L) were synthesized by the reactions of the corresponding organic ligands with MCl2-nH(2)O. The resulting complexes have the composition LMCl2 (M = Cu(.)or Ni) or L2MCl2 (M = Co). The reactions with N(3)-unsubstituted thiohydantoins afford complexes containing four-membered metallacycles, in which the metal ion is coordinated by the S and N(3) atoms of the thiohydantoin ligand. The reactions of N(3)-substituted thiohydantoins give complexes in which the S and N(l) atoms are involved in coordination. Study by IR spectroscopy demonstrated that the pyridine nitrogen atom is not involved in coordination. Based on the results of electrochemical study of the ligands and complexes by cyclic voltammetry and calculation of their frontier orbitals by the PM3(tm) method, the mechanism of oxidation and reduction of these compounds was proposed. In the first reduction and oxidation steps, the metal atom in the copper and nickel complexes remains, apparently, intact, and these processes occur with the involvement of the ligand fragments, viz., the coordinated thiohydantoin ligand and chloride anion, respectively. In the cobalt complexes, the first reduction step occurs at the ligand; the first oxidation state, at the metal atom. Measurements of the contact angle of aqueous wetting and electrochemical study demonstrated that carboxy-containing 2-thiohydantoins and their complexes can be adsorbed on the cystamine-modified gold surface. The structures of the complexes on the surface differ from the structures of these complexes in solution.