Synthetic, structural and kinetic studies on the binding of cyclohexane-1,2-bis(4-methyl-3-thiosemicarbazone) to divalent metal ions (Co, Ni, Cu, Zn or Cd)

Dalton Trans. 2009 Jan 21:(3):564-70. doi: 10.1039/b814852j. Epub 2008 Nov 12.

Abstract

The reactions of cyclohexane-1,2-bis(4-methyl-3-thiosemicarbazone) (CHMTSC) with MCl2 (M = Co, Ni, Cu or Zn) and Cd(NO3)2 have been shown to produce complexes in which the thiosemicarbazone has been doubly deprotonated [[M(CHMTSC - 2H+)] (M = Co, Ni or Ni)], analogous to those reported earlier with other Schiff base thiosemicarbazones. However, with ZnCl2 and Cd(NO3)2, the complexes isolated are [ZnCl(CHMTSC)]Cl and [Cd(NO3)(CHMTSC)]NO3, containing the protonated forms of the ligand, which have been characterised by X-ray crystallography, as has free CHMTSC. The kinetics of the reactions between CHMTSC and all the various metal salts have been determined by stopped-flow spectrophotometry. In all cases, the reactions are complete on the seconds timescale. The reactions exhibit a first-order dependence on the concentration of metal salt and a first-order dependence on the concentration of CHMTSC. The thermodynamic and kinetic factors influencing the protonation state of the coordinated thiosemicarbazone are discussed.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Cadmium / chemistry
  • Chlorides / chemistry
  • Cobalt / chemistry
  • Copper / chemistry
  • Crystallography, X-Ray
  • Cyclohexanes / chemistry*
  • Ions
  • Kinetics
  • Metals / chemistry*
  • Models, Chemical
  • Molecular Conformation
  • Nickel / chemistry
  • Temperature
  • Thiosemicarbazones / chemistry*
  • Zinc / chemistry
  • Zinc Compounds / chemistry

Substances

  • Chlorides
  • Cyclohexanes
  • Ions
  • Metals
  • Thiosemicarbazones
  • Zinc Compounds
  • cyclohexane-1,2-bis(4-methyl-3-thiosemicarbazone)
  • Cadmium
  • Cobalt
  • Cyclohexane
  • Copper
  • Nickel
  • zinc chloride
  • Zinc