Catalytic B–C Coupling by Si/B Exchange: A Versatile Route to π‑Conjugated Organoborane Molecules, Oligomers, and Polymers

Conjugated organoboranes have emerged as attractive hybrid materials for optoelectronic applications. Herein, a highly efficient, environmentally benign catalytic B–C bond formation method is presented that uses organosilicon compounds, dibromoboranes, and the metal-free organocatalyst Me₃SiNTf₂. This Si/B exchange approach has been successfully applied to the synthesis of arylborane molecules 4a–c, oligomers 8a,b, and polymers 8a′,b′. Photophysical investigations, supported by TD-DFT calculations, reveal highly effective π-conjugation in thienyl- and furylborane species; the latter are also highly emissive.