Abstract
The chelation behavior of some =N(1) and NH(4) thiosemicarbazones towards copper(II) ions has been investigated. The isolated complexes are characterized by elemental analysis, magnetic moment, electronic, IR, ESR and ms spectra, and by thermal and voltammetric measurements. The substituents on =N(1) and/or NH(4) thiosemicarbazones and the log K values of the ligands play an important role in complex formation. The IR spectra showed that the reagents HAT, HAET, HAPT, HApClPT, H
2
ST and HBT are deprotonated in the complexes and act as mononegative SN donors; H
2
SET, H
2
SpClPT, H
2
HyMBPT and H
2
HyMBpClPT, as binegative NSO donors while H
2
SPT is a mononegative NSO donor. The ESR spectra of the complexes are quite similar and exhibit axially symmetric g-tensor parameters with g
||
> g
⊥
> 2.0023. The loss of thiol and/or hydroxyl hydrogen was confirmed from potentiometric titrations of the ligands and their copper(II) complexes. The protonation constants of the ligands as well as the stability constants of their Cu(II) complexes were calculated. Thermogravimetric analysis of the complexes suggests different decomposition steps. The Coats-Redfern and Horowitz-Metzger equations have been used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition steps of some complexes. The redox properties, nature of the electroactive species and the stability of the complexes towards oxidation are strongly dependent on the substituents on the precursor NH(4) thiosemicarbazone. The redox data are discussed in terms of the kinetic parameters and the reaction mechanism.