The catalytic activity of the NHI-substituted aluminum hydrides {L Mes NAlH 2 } 2 (1a), {L Dip NAlH 2 } 2 (1b), {L Mes NAl(H)OTf} 2 (2a), and {L Dip NAl(H)OTf} 2 (2b) in the hydroboration of terminal alkynes (for 1), as well as carbonyl compounds (for 2) with pinacolborane (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) is investigated (L Mes N = 1,3-dimesityl-imidazolin-2-imino, Mes = 2,4,6-trimethylphenyl, L Dip N = 1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-imino, Tf = triflyl).