Synthesis of closo- and nido-biscarboranes with rigid unsaturated linkers as precursors to linear metallacarborane-based molecular rods.

Several biscarborane-type derivatives of 8-iodo-1,2-dicarba-closo-dodecaborane (1), suitable as the precursors of linear metallacarborane-based molecular rods, were prepared. The synthesized closo-compounds contained two carborane moieties connected through a rigid linear unsaturated linker. The linkers were based on ethynylene and para-phenylene fragments and their combinations. The deboronation of all reported closo-compounds was selective and afforded nido-products with open pentagonal faces on opposite sides of the molecule, parallel to each other and perpendicular to the main molecular axis. All of the closo and nido products were characterized by a variety of physical methods (NMR, HRMS, IR). The structures of closo-carboranes 3, 6, 9, and 14 and nido-carboranes 15 and 17 were established by X-ray diffraction.