“…The development of novel polymerization methods and related processes is of great importance in enriching the diversity of polymer science and accessing various functional materials. â As one of the most important families of functional materials, organosilicon polymers have been widely applied in adhesives, coatings, ceramics, moldings, and sealing materials. â In particular, polycarbosilanes containing SiâC bonds in polymer backbones have received extensive investigation due to their low toxicity, high chain flexibility, and excellent thermal and oxidative resistance. ,â The catalytic synthesis of polycarbosilanes traditionally relies on the hydrosilylation polymerization of alkenes and silanes, typically by Pt-based catalysts such as Speierâs and Karstedtâs catalysts. â More recently, rare earth metal catalysis, early transition-metal catalysis, , borane-based catalysis, , and photocatalysis , have emerged as new tools (Scheme a). In contrast to widely investigated hydrosilylation polymerization of alkenes, in which regioselectivity issues should be taken into consideration, other strategies are much less exploited and developed …”