[(Ph)<sub>3</sub>PBr][Br<sub>7</sub>], [(Bz)(Ph)<sub>3</sub>P]<sub>2</sub>[Br<sub>8</sub>], [(<i>n</i>-Bu)<sub>3</sub>MeN]<sub>2</sub>[Br<sub>20</sub>], [C<sub>4</sub>MPyr]<sub>2</sub>[Br<sub>20</sub>], and [(Ph)<sub>3</sub>PCl]<sub>2</sub>[Cl<sub>2</sub>I<sub>14</sub>]: Extending the Horizon of Polyhalides via Synthesis in Ionic Liquids
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The five polyhalides [(Ph)3PBr][Br7], [(Bz)(Ph)3P]2[Br8], [(n-Bu)3MeN]2[Br20], [C4MPyr]2[Br20] ([C4MPyr] = N-butyl-N-methylpyrrolidinium), and [(Ph)3PCl]2[Cl2I14] were prepared by the reaction of dibromine and iodine monochloride in ionic liquids. The compounds [(Ph)3PBr][Br7] and [(Bz)(Ph)3P]2[Br8] contain discrete pyramidal [Br7]− and Z-shaped [Br8]2– polybromide anions. [(n-Bu)3MeN]2[Br20] and [C4MPyr]2[Br20] exhibit new infinite two- and three-dimensional polybromide networks and contain the highest percentage of dibromine ever observed in a compound. [(Ph)3PCl]2[Cl2I14] also consists of a three-dimensional network and is the first example of an infinite polyiodine chloride. All compounds were obtained from ionic liquids as the solvent that, on the one hand, guarantees for a high stability against strongly oxidizing Br2 and ICl and that, on the other hand, reduces the high volatility of the molecular halogens.
