Attempted oxidative addition of halogens to (isocyanide)gold(I) complexes

Daniel Schneider, Oliver Schuster, Hubert Schmidbaur

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32 Scopus citations


Oxidative addition of bromine to an (isocyanide)gold(I) bromide proceeds smoothly to give the corresponding (isocyanide)gold(III) tribromide as demonstrated by the preparation and structural characterization of ( tBuNC)AuBr3. By contrast, no oxidative addition of iodine is observed with (isocyanide)gold(I) iodides. Ligand redistribution to give ionic compounds and intercalation of I2 molecules occurs instead as shown for [(tBuNC)2Au]+[AuI2] - (I2)- In crystals of this product, linear chains of almost equidistant gold atoms of alternating cations and anions feature interionic aurophilic bonding [Au- - -Au 3.2674(5) and 3.3056(5) Å]. The iodine molecules form polyhalide bridges between the columns of complex ions. From the reaction mixture of (cHexNC)AuI and an excess of iodine a crystalline pentaiodide, [(cHexNC)2Au]+[I 5]-, has been isolated in which the cations are imbedded between corrugated sheets of the polyhalide anions.

Original languageEnglish
Pages (from-to)3547-3551
Number of pages5
Issue number14
StatePublished - 4 Jul 2005
Externally publishedYes


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