Elusive Silane–Alane Complex [SiH⋅⋅⋅Al]: Isolation, Characterization, and Multifaceted Frustrated Lewis Pair Type Catalysis

The super acidity of the unsolvated Al(C 6 F 5 ) 3 enabled isolation of the elusive silane–alane complex [SiH⋅⋅⋅Al], which was structurally characterized by spectroscopic and X‐ray diffraction methods. The Janus‐like nature of this adduct, coupled with strong silane activation, effects multifaceted frustrated‐Lewis‐pair‐type catalysis. When compared with the silane–borane system, the silane–alane system offers unique features or clear advantages in the four types of catalytic transformations examined in this study, including: ligand redistribution of tertiary silanes into secondary and quaternary silanes, polymerization of conjugated polar alkenes, hydrosilylation of unactivated alkenes, and hydrodefluorination of fluoroalkanes.