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Malinowski PJ, Himmel D, Krossing I. Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag(+) /X2 (X=Cl, Br, I) System. Angew Chem Int Ed Engl. 2016;55(32):9262-6doi: 10.1002/anie.201603913.
Malinowski, P. J., Himmel, D., & Krossing, I. (2016). Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag(+) /X2 (X=Cl, Br, I) System. Angewandte Chemie (International ed. in English), 55(32), 9262-6. https://doi.org/10.1002/anie.201603913
Malinowski, Przemysław J, et al. "Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag(+) /X2 (X=Cl, Br, I) System." Angewandte Chemie (International ed. in English) vol. 55,32 (2016): 9262-6. doi: https://doi.org/10.1002/anie.201603913
Malinowski PJ, Himmel D, Krossing I. Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag(+) /X2 (X=Cl, Br, I) System. Angew Chem Int Ed Engl. 2016 Aug 01;55(32):9262-6. doi: 10.1002/anie.201603913. Epub 2016 Jul 13. PMID: 27411163.
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Angew Chem Int Ed Engl. 2016 Aug 01;55(32):9262-6. doi: 10.1002/anie.201603913. Epub 2016 Jul 13.

Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag(+) /X2 (X=Cl, Br, I) System.

Angewandte Chemie (International ed. in English)

Przemysław J Malinowski, Daniel Himmel, Ingo Krossing

Affiliations

  1. Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg, Freiburg i. Br., Germany.
  2. Centre of New Technologies, University of Warsaw, Warsaw, Poland.
  3. Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg, Freiburg i. Br., Germany. [email protected].

PMID: 27411163 DOI: 10.1002/anie.201603913

Abstract

The synergistic Ag(+) /X2 system (X=Cl, Br, I) is a very strong, but ill-defined oxidant-more powerful than X2 or Ag(+) alone. Intermediates for its action may include [Agm (X2 )n ](m+) complexes. Here, we report on an unexpectedly variable coordination chemistry of diiodine towards this direction: (A)Ag-I2 -Ag(A), [Ag2 (I2 )4 ](2+) (A(-) )2 and [Ag2 (I2 )6 ](2+) (A(-) )2 ⋅(I2 )x≈0.65 form by reaction of Ag(A) (A=Al(OR(F) )4 ; R(F) =C(CF3 )3 ) with diiodine (single crystal/powder XRD, Raman spectra and quantum-mechanical calculations). The molecular (A)Ag-I2 -Ag(A) is ideally set up to act as a 2 e(-) oxidant with stoichiometric formation of 2 AgI and 2 A(-) . Preliminary reactivity tests proved this (A)Ag-I2 -Ag(A) starting material to oxidize n-C5 H12 , C3 H8 , CH2 Cl2 , P4 or S8 at room temperature. A rough estimate of its electron affinity places it amongst very strong oxidizers like MF6 (M=4d metals). This suggests that (A)Ag-I2 -Ag(A) will serve as an easily in bulk accessible, well-defined, and very potent oxidant with multiple applications.

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: donor-acceptor systems; oxidation; structure elucdiation; vibrational spectroscopy; weakly coordinating anions

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