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Przemysaw J. Malinowski Daniel Himmel Ingo Krossing 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(32):9408-9412
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. 相似文献
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