Rare-Earth-Catalyzed Hydrosilylation and Dehydrogenative Coupling of Hydrosilanes

Activation of Si–H bonds with rare-earth complexes could generate the highly reactive rare-earth hydrides or silyl complexes, which are key intermediates for hydrosilylation and cross-coupling reactions. This Account summarizes the recent advances in the rare-earth-catalyzed hydrosilylation of unsaturated substrates and dehydrogenative coupling of hydrosilanes with amines in our laboratory. The results demonstrated that rare-earth catalysts are unique in their reactivity and selectivity, enabling some unprecedented reactions. 1 Introduction 2 Dehydrogenative Coupling of Hydrosilanes with Amines 3 Catalytic Dehydrogenative Coupling of Hydrosilanes with Amines 4 Catalytic Hydrosilylation of Terminal Alkenes and Polymerization of Styrene 5 Catalytic Hydrosilylation of Internal Alkenes 6 Catalytic Dihydrosilylation of Internal Alkynes 7 Conclusions and Outlook