Peroxide Coordination of Tellurium in Aqueous Solutions

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

doi:10.1002/chem.201503614

Peroxide Coordination of Tellurium in Aqueous Solutions

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

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

23 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 language	American English
Pages (from-to)	2980-2986
Number of pages	7
Journal	Chemistry - A European Journal
Volume	22
Issue number	9
DOIs	https://doi.org/10.1002/chem.201503614
State	Published - 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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10.1002/chem.201503614

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@article{468dbd4a0bd74e6292fc3d308a995ae6,

title = "Peroxide Coordination of Tellurium in Aqueous Solutions",

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.",

keywords = "bridging ligands, main group elements, peroxides, peroxido ligands, tellurium",

author = "Mikhaylov, {Alexey A.} and Medvedev, {Alexander G.} and Churakov, {Andrei V.} and Grishanov, {Dmitry A.} and Prikhodchenko, {Petr V.} and Ovadia Lev",

note = "Publisher Copyright: {\textcopyright} 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2016",

month = feb,

day = "24",

doi = "10.1002/chem.201503614",

language = "American English",

volume = "22",

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T1 - Peroxide Coordination of Tellurium in Aqueous Solutions

AU - Mikhaylov, Alexey A.

AU - Medvedev, Alexander G.

AU - Churakov, Andrei V.

AU - Grishanov, Dmitry A.

AU - Prikhodchenko, Petr V.

AU - Lev, Ovadia

PY - 2016/2/24

Y1 - 2016/2/24

N2 - 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.

AB - 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.

KW - bridging ligands

KW - main group elements

KW - peroxides

KW - peroxido ligands

KW - tellurium

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DO - 10.1002/chem.201503614

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Peroxide Coordination of Tellurium in Aqueous Solutions

Abstract

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Keywords

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