Cobalt-Catalyzed Hydrosilylation Polymerization for the Synthesis of Linear Polycarbosilanes

Polycarbosilanes are unique precursors in the preparation of silicon carbide ceramics and silicon carbide fibers. The conventional production is carried out upon harsh reaction conditions with a low molecular weight, while the catalytic hydrosilylation polymerization typically relies on noble metal catalysis. We herein report a cobalt-catalyzed hydrosilylation polymerization of dienes and bis-silanes, providing an alternative strategy that enabled the efficient synthesis of linear polycarbosilanes. A broad scope of polycarbosilanes was delivered with up to 25 kDa molecular weight, narrow dispersity, and decent thermal stability. The further functionalization of polycarbosilanes was accessible, while the kinetic process of polymerization was also investigated. Moreover, the introduction of chirality into the polymeric backbone was available, suggesting the application prospects of using polycarbosilanes as chiral organic optoelectronic materials.