Divalent nickel complexes of thiosemicarbazone based on 5-bromosalicylaldehyde and triphenylphosphine: Experimental and theoretical characterization

Guveli S., Ozdemir N., Ulkuseven B., Bal-Demirci T.

POLYHEDRON, vol.113, pp.16-24, 2016 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 113
  • Publication Date: 2016
  • Doi Number: 10.1016/j.poly.2016.03.057
  • Journal Name: POLYHEDRON
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.16-24
  • Istanbul University Affiliated: Yes


Two nickel(II) complexes containing 5-bromosalicylidene-N-methyl-S-methyl-isothiosemicarbazone (H(2)SMeNMeTsc) and 5-bromosalicylidene-N-methyl-thiosemicarbazone (H(2)NMeTsc) with triphenylphosphine were synthesized. The compounds were characterized by elemental analysis, IR, H-1 NMR and UV-Vis spectroscopies, and their structures were determined by single crystal X-ray diffraction technique. Theoretical characterization of the compounds was carried out using the density functional theory (DFF/B3LYP) method with 6-311G(d,p) basis set for the C, H, Br, N, O, P, S atoms and LANL2DZ pseudo-potential for Ni atom, and the results were checked against the experimental data. Electronic absorption spectra of the compounds have also been obtained using the time-dependent density functional theory (TD-DFT) formalism at the same level. The coordination geometry around Ni-II in the two complexes is distorted square-planar geometry. While the thiosemicarbazone ligand is coordinated to nickel through ONN mode in [Ni(SMeNMeTsc)(PPh3)]center dot PPh3, it is bound to the metal as dianionic ONS donors in [Ni(NMeTsc)(PPh3)]. The consistency between theoretical and experimental values is good in general. (C) 2016 Elsevier Ltd. All rights reserved.