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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)

Lookup NU author(s): Emeritus Professor Bill CleggORCiD, Dr Ross Harrington, Professor Richard Henderson

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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 metadata

Author(s): Al-Karawi AJM, Clegg W, Harrington RW, Henderson RA

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2009

Issue: 3

Pages: 564-570

Print publication date: 01/01/2009

ISSN (print): 1477-9234

ISSN (electronic): 1477-9226

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/b814852j

DOI: 10.1039/b814852j

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