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Angewandte 1: Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag+/X2 (X=Cl, Br, I) System

Doppelschlag in der "Angewandten Chemie" Teil 1: In einer Ausgabe der Angewandten wurden gleich zwei Publikationen unserer Forschergruppe veröffentlicht!

Dr. Przemysław J. Malinowski, Dr. Daniel Himmel, Prof. Dr. Ingo Krossing

 

 

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(ORF)4; RF=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-C5H12, C3H8, CH2Cl2, 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.

DOI: 10.1002/anie.201603913

 

 

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