New Synthetic Strategies for Structured Silicones Using B(C6F5)3

The dehydrocarbonative condensation of alkoxysilanes + hydrosilanes in the presence of the Lewis acid catalyst B(C6F5)3 (R3SiOR′ + HSiR3′′ → R3SiOSiR3′′ + R′H) – described throughout this review as the Piers-Rubinsztajn reaction – provides a new, mild strategy for the controlled synthesis of silicones. In this review we examine the mechanistic parameters that control the reaction, and outline the types of accessible small molecules, linear, branched, and cross-linked materials (resins and elastomers) that can be prepared using this and related reactions.