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

Date

2014-05-28

Author

Ozbek, Ozge
ÖZALP YAMAN, Şeniz
Özkan, İlker
Önal, Ahmet Muhtar
İŞÇİ, HÜSEYİN

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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.

Subject Keywords

Diplatinum Coordination Compounds, Electronic Absorption Spectra, Spectroelectrochemistry, Molecular Orbital Energy Level Diagram, DFT Calculations

URI

https://hdl.handle.net/11511/32598

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Graduate School of Natural and Applied Sciences, Article