Metal Assisted Synthesis of Cationic Sulfidobismuth Cubanes in Ionic Liquids.

Bi S was dissolved in the presence of either AuCl/PtCl or AgCl in the ionic liquids [BMIm]Cl ⋅ xAlCl (BMIm=1-n-butyl-3-methylimidazolium; x=4-4.3) through annealing the mixtures at 180 or 200 °C. Upon cooling to room temperature, orange, air-sensitive crystals of [BMIm](Bi S )[AlCl ] (1) or Ag(Bi S )[S(AlCl ) ] [AlCl ] (2) precipitated, respectively. 1 did not form in the absence of AuCl/PtCl , suggesting an essential role of the metal cations. X-ray diffraction on single-crystals of 1 revealed a monoclinic crystal structure that contains (Bi S ) heterocubanes and [AlCl ] tetrahedra as well as [BMIm] cations. The intercalation of the ionic liquid was confirmed via solid state NMR spectroscopy, revealing unusual coupling behavior. The crystal structure of 2 consists of (Bi S ) spiro-dicubanes, [S(AlCl ) ] tetrahedra triples, isolated [AlCl ] tetrahedra, and heavily disordered silver(I) cations. No cation ordering took place in 2 upon slow cooling to 100 K.