X-type silyl ligands for transition-metal catalysis.

Given the critical importance of novel ligand development for transition-metal (TM) catalysis, as well as the resurgence of the field of organosilicon chemistry and silyl ligands, to summarize the topic of X-type silyl ligands for TM catalysis is highly attractive and timely. This review particularly emphasizes the unique σ-donating characteristics and -effects of silyl ligands, highlighting their crucial roles in enhancing the reactivity and selectivity of various catalytic reactions, including small molecule activation, Kumada cross-coupling, hydrofunctionalization, C-H functionalization, and dehydrogenative Si-O coupling reactions. Additionally, future developments in this field are also provided, which would inspire new insights and applications in catalytic synthetic chemistry.