Syntheses, characterization of and studies on the electrochemical behaviour of ferrocenyl dithiophosphonates and 4-methoxyphenyl dithiophosphonates

SAĞLAM E. G., Erden S., Tutsak O., ESKİKÖY BAYRAKTEPE D., Durmus Z. Y., DAL H., ...More

PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS, vol.192, no.3, pp.322-329, 2017 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 192 Issue: 3
  • Publication Date: 2017
  • Doi Number: 10.1080/10426507.2016.1238368
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Index Chemicus (IC)
  • Page Numbers: pp.322-329
  • Keywords: Ferrocenyl Lawesson reagent, Lawesson reagent, ferrocenyl-dithiophosphonate, thio-phosphorus compounds, cyclic voltammetry, COORDINATION CHEMISTRY, COMPLEXES, LIGANDS, ACID, FE(ETA(5)-C5H4)(ETA(5)-C5H5), FERROCENYLDITHIOPHOSPHONATES, DERIVATIVES, METALS, NMR, END
  • Anadolu University Affiliated: No


Some 1,3-dithiadiphosphetane 2,4-disulfides (X2P2S4, X: Fc, FcLR; X: CH3OC6H4, LR) were allowed to react with alcohols to obtain dithiophosphonic acids (X(OR)PS2H). These were converted to the corresponding ammonium salts. The salts were of the structures [Fc(OR)PS2](-)[NH4](+), R: 3-methyl-1-butyl- for I; 1-phenyl-1-propyl- for II; 3-pentyl- for III; 3-phenyl-1-propyl- for IV and [CH3OC6H4(OR)PS2](-)[NH4](+), R: 3-methyl-1-butyl- for V and 1-phenyl-1-propyl- for VI. To the best of our knowledge, all the compounds except V were prepared for the first time.The compounds synthesized were characterized by elemental analysis, NMR (H-1, C-13, P-31), MS, FTIR, and Raman spectroscopies. Electrochemical behaviors of I-VI at disposable pencil graphite electrode (PGE) were investigated by using cyclic voltammetry (CV) and square-wave voltammetry (SWV). Adsorption and diffusion patterns of all the compounds on the PGE were also studied.Two electroactive groups were identified in the compounds I-IV and only one in V and VI. The ferrocenyl groups of I-IV were oxidized at around 0.4V. The same compounds display a second, more intense CV band at 0.8V. The corresponding band for the compounds V-VI appears at around 0.6V with a much weaker intensity. It is suggested that the ferrocenyl group introduced into the structures stabilizes the radical species formed as the product of the oxidation of the dithiophosphonato group.