Peroxide Coordination of Tellurium in Aqueous Solutions

Alexey A. Mikhaylov, Alexander G. Medvedev, Andrei V. Churakov, Dmitry A. Grishanov, Petr V. Prikhodchenko, Ovadia Lev

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26 Scopus citations

Abstract

Tellurium-peroxo complexes in aqueous solutions have never been reported. In this work, ammonium peroxotellurates (NH4)4Te2(μ-OO)2(μ-O)O4(OH)2 (1) and (NH4)5Te2(μ-OO)2(μ-O)O5(OH)1.28 H2Ȯ0.72 H2O2 (2) were isolated from 5 % hydrogen peroxide aqueous solutions of ammonium tellurate and characterized by single-crystal and powder X-ray diffraction analysis, by Raman spectroscopy and thermal analysis. The crystal structure of 1 comprises ammonium cations and a symmetric binuclear peroxotellurate anion [Te2(μ-OO)2(μ-O)O4(OH)2]4-. The structure of 2 consists of an unsymmetrical [Te2(μ-OO)2(μ-O)O5(OH)]5- anion, ammonium cations, hydrogen peroxide, and water. Peroxotellurate anions in both 1 and 2 contain a binuclear Te2(μ-OO)2(μ-O) fragment with one μ-oxo- and two μ-peroxo bridging groups. 125Te NMR spectroscopic analysis shows that the peroxo bridged bitellurate anions are the dominant species in solution, with 3-40 %wt H2O2 and for pH values above 9. DFT calculations of the peroxotellurate anion confirm its higher thermodynamic stability compared with those of the oxotellurate analogues. This is the first direct evidence for tellurium-peroxide coordination in any aqueous system and the first report of inorganic tellurium-peroxo complexes. General features common to all reported p-block element peroxides could be discerned by the characterization of aqueous and crystalline peroxotellurates. Isolating an intermediate: Ammonium peroxotellurates (NH4)4Te2(μ-OO)2(μ-O)O4(OH)2 and (NH4)5Te2(μ-OO)2(μ-O)O5(OH)1.28 H2Ȯ0.72 H2O2 (see figure) were isolated from 5 % hydrogen peroxide aqueous solutions of ammonium tellurate and characterized by single-crystal and powder X-ray diffraction studies and by Raman spectroscopy and thermal analysis.

Original languageAmerican English
Pages (from-to)2980-2986
Number of pages7
JournalChemistry - A European Journal
Volume22
Issue number9
DOIs
StatePublished - 24 Feb 2016

Bibliographical note

Publisher Copyright:
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords

  • bridging ligands
  • main group elements
  • peroxides
  • peroxido ligands
  • tellurium

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