• 12-B heteropolyanions as ligands: Synthesis, spectral characterisation and solution studies of [MnIVThMo12O42]4−, [MnIVUMo12O42]4− and [VIVCeMo12O42]4−

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      https://www.ias.ac.in/article/fulltext/jcsc/110/01/0007-0019

    • Keywords

       

      12-B heteropolyanion; manganese; vanadium; synthesis; EPR

    • Abstract

       

      Interaction of 12-B heteropolyanions, [XMo12O42]8−, whereX=Ce, Th and U, with tetravalent transition metal ions MnIV and VIV results in the formation of three well defined complexes, viz., (NH4)4[MnIVThMo12O42]·10H2O (I), (NH4)4[MnIVUMo12O42]·8H2O (II) and (NH4)4[VIVCeMo12O42]·8H2O (III), which are characterised by IR, Raman and EPR spectroscopies. Negative shift in the stretching frequency of Mo-Ot bond in IR spectra and appearance of a strong band at 818 cm−1 in Raman spectra support the formation of these complexes. EPR spectra of complexes (I) and (II) show a predominant signal atg=4 and a weak signal atg=2 (with hyperfine coupling from55Mn), characteristic of d3 system, (S=3/2 andI=5/2) with large zero field splitting, showing distortion from octahedral symmetry. EPR parameters of the vanadium complex (III) show thed-electron to be more localised on vanadium(IV) supporting the formulation of vanadium not to be a part of the “Mo12” unit. The oxidising property of complexes (I) and (II) is studied using glucose as the substrate.

    • Author Affiliations

       

      R Murugesan1 T Jeyabalan2 3 P Sami2 4 A Shunmugasundaram2

      1. School of Chemistry, Madurai Kamaraj University, Madurai - 625 021, India
      2. Department of Chemistry, VHNSN College, Virudhunganar - 626 001, India
      3. Department of Chemistry, Priyadarshini Engineering College, Vaniyambadi - 635 851, India
      4. Department of Chemistry, Dr Sivanthi Aditanar College of Engineering, Tiruchendur - 628 215, India
    • Dates

       
  • Journal of Chemical Sciences | News

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