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Activity of oxidative coupling catalysts with carbon disulphide to generate the first new redox dithiocarbonato moiety [(Pip)nCuX]4(CS2O)2

Author Affiliations

  • 1Chemistry Department, Faculty of Science, Alexandria University, Alexandria, Egypt
  • 2Chemistry Department, Faculty of Science, Alexandria University, Alexandria, Egypt and Chemistry Department, Faculty of Science, University of Jeddah, Jeddah, Saudi Arabia
  • 3Chemistry Department, Faculty of Science, Alexandria University, Alexandria, Egypt
  • 4Chemistry Department, Faculty of Science, Alexandria University, Alexandria, Egypt

Res.J.chem.sci., Volume 8, Issue (7), Pages 1-8, July,18 (2018)


A new series of tetranuclear [(Pip)nCuX]4(CS2O)2, where Pip = Piperidine, n = 1 or 2 X = Cl or Br, are obtained according to the reaction of the lewis acid [(Pip)nCuX]4O2 towards the lewis base CS2 at room temperature. The synthesised compounds are characterized using molecular weight determination, elemental analysis and spectral techniques (FTIR, UV/Vis. and EPR). The FTIR spectral data showed that CS2O2- group acts as a dibasic bidentate or tridentate bridging ligand for n=2 or 1, respectively. The bridging CS2O2- containing tetranuclear complexes display a CS2O2- - Cu2+ Charge transfer band at 430-410nm for all [(Pip)nCuX]4(CS2O)2 complexes with molar absorptivity varying from 4000 to 14000M- cm-1. Bidentate bridging anion (CS2O)2- in [(Pip)2CuX]4(CS2O)2 shows another charge transfer with Cu(II), at 605nm and 575nm with molecular absorptivities 810 and 970M-1cm-1 for X=Cl and Br respectively. The electrochemical behavior of the new tetranuclear complexes are studied where the dithiocarbonato anion in [(Pip)nCuX]4(CS2O)2 is found to be electrochemically active showing quasi-reversible peaks at a more positive potentials, when compared with Cu(II) centres. The complexes are shown to be catalytically inactive toward the oxidation of 2,6-dimethyl phenol unlike their oxo and carbonato analogues.


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