Spectroelectrochemical investigations of pyrimidine-2-thionato-bridged binuclear platinum(III) complexes

Ozbek O., ÖZALP YAMAN Ş., ÖZKAN İ., ÖNAL A. M., İŞÇİ H.

POLYHEDRON, cilt.74, ss.122-128, 2014 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 74
  • Basım Tarihi: 2014
  • Doi Numarası: 10.1016/j.poly.2014.02.046
  • Dergi Adı: POLYHEDRON
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.122-128
  • Orta Doğu Teknik Üniversitesi Adresli: Evet

Özet

The electrochemical behavior of the binuclear platinum(III-III) complexes [Pt-2(C4H3N2S)(4)X-2] (C4H3N2S- = pyrimidine-2-thionate; X- = Cl--,Cl- Br--,Br- I-) have been studied by cyclic voltammetry and insitu spectroelectrochemistry in an acetonitrile-tetrabutylammonium tetrafluoroborate solventelectrolyte couple. An irreversible metal based reduction appears during the cathodic scan for each of the three complexes. The changes in UV-Vis spectra observed in-situ during the reductive electrolysis indicate that all three complexes give the same product, [Pt-2(C4H3N2S)(4)], with a Pt(II)-Pt(II) system. The changes in the reduction potentials of the complexes on changing the axial ligands are interpreted by the changes in the energy of the LUMO level, which is determined by the degree of sigma- and it-interactions of the axial halide ligands with the metal atoms. DFT (B3LYP/LanL2DZ) calculations support our experimental data. (c) 2014 Elsevier Ltd. All rights reserved.