Syntheses, spectral, thermal and electrochemical studies of 3-carboxylacetonehydroxamic acid and its iron(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes


YILMAZ F., Yilmaz V. T. , Topcu S., Menek N.

JOURNAL OF COORDINATION CHEMISTRY, vol.56, no.10, pp.903-911, 2003 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 56 Issue: 10
  • Publication Date: 2003
  • Doi Number: 10.1080/0095897031000135315
  • Journal Name: JOURNAL OF COORDINATION CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.903-911
  • Keywords: 3-carboxylacetonehydroxamic acid, metal complexes, square wave voltammetry, cyclic voltammetry, TRANSITION-METAL COMPLEXES, HYDROXAMIC ACIDS, ACETYLSALICYLHYDROXAMIC ACID, SALICYLHYDROXAMIC ACID, AQUEOUS-SOLUTION, LIGAND, COORDINATION, KINETICS, THERMODYNAMICS, DISSOCIATION
  • Karadeniz Technical University Affiliated: No

Abstract

3-Carboxylacetonehydroxamic acid (CAHA) and its iron(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes were synthesized and characterized by elemental analysis, UV-Vis and IR spectra and magnetic susceptibility. The pK(a1) and pK(a2) Values of the ligand in aqueous solution were found to be 6.5+/-0.1 and 8.6+/-0.1, which correspond to dissociation of carboxyl and hydroxamic protons, respectively. The dianion CAH acts as a tetradentate ligand through the hydroxamate and carboxylate groups and coordinates to the divalent metal ions, forming coordination polymers with a metal-to-ligand ratio of 1 : 1 in the solid state. FTIR spectra and thermal decomposition of the ligand and its metal complexes were recorded and briefly discussed. The electrochemical behavior of the complexes was investigated by square wave voltammetry and cyclic voltammetry at neutral pH. In contrast to the solid state, the iron(II) and copper(II) cations form stable complex species with a metal-to-ligand ratio of 1 : 2 in solution. The iron(II), cobalt(II) and nickel(II) complexes show two-electron irreversible reduction behavior, while the copper(II) and zinc(II) complexes undergo quasi-reversible and reversible electrode reactions, respectively. The stability constants of the complexes were determined by square wave voltammetry.