Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag+/X2 (X=Cl,Br, I) System |
| |
| Authors: | Dr Przemys?aw J Malinowski Dr Daniel Himmel Prof?Dr Ingo Krossing |
| |
| Affiliation: | 1. Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universit?t Freiburg, Freiburg i. Br., Germany;2. Centre of New Technologies, University of Warsaw, Warsaw, Poland |
| |
| 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. |
| |
| Keywords: | donor– acceptor systems oxidation structure elucdiation vibrational spectroscopy weakly coordinating anions |
|
|
