Bridged Heterocyclium Dicationic closo-Icosahedral Perfluoroborane, Borane, and Carborane Salts via Aqueous, Open-Air Benchtop Synthesis

Thirteen bridged triazolium and imidazolium dicationic salts, which uniquely pair closo-icosahedral perfluoroborane [B(12)F(12)](2-), borane [B(12)H(12)](2-), or carborane [CB(11)H(12)](-) anionic species with unsaturated bridged heterocyclium dications, were synthesized using an aqueous benchtop method. This considerably extends the scope of a reported aqueous synthesis of binary [heterocyclium](2)[B(12)H(12)] and [heterocyclium][CB(11)H(12)] salts. Also, the one-step preparation of five new precursor bridged heterocyclium dicationic dihalide salts using conventional procedures and in one case a microwave-assisted method Is described.