Borane-Catalyzed Si–H Activation Routes to Polysilanes Containing Thiolato Side Chains

Dehydrocoupling and hydrosilation reactions of the Si–H bonds in poly­(phenylsilane) catalyzed by B­(C₆F₅)₃ allow the preparation of new polymers containing both Si–H and Si–SR side chains. This postpolymerization modification takes place without any observable competing Si–Si bond cleavage, unlike other Lewis acid, transition-metal, or radical mediated routes. The −SR-functionalized polymers have been characterized by GPC, IR, UV–vis, elemental analysis, and ¹H, ¹³C, and ²⁹Si NMR