Following stoichiometric reactivity, and inspired by the Ln/Al heterobimetallic hydride hydroalumination catalyst [V] (Figure ), the applicability of 2-Ln in catalysis was examined to further investigate the cooperative reactivity between the two metal centres. Recently the catalytic dehydrocoupling of [Me2HN•BH3] has attracted significant interest, owing to the utility of amineboranes in hydrogen storage and as precursors to boron-nitride materials. Ln hydrides and aluminium hydrides have both been reported to catalyse the dehydrocoupling of [Me2HN•BH3] at elevated temperatures, thus providing a good basis for this preliminary study. The dehydrocoupling of [Me2HN•BH3] by 10 mol% 2-Ln (Ln = Y, Sm, Dy, Yb) proceeds at room temperature to yield [Me2N•BH2]2 as the major product (Table , see ESI for further details). Notable differences were found across the 2-Ln series, with consumption of amine-borane occurring most efficiently in the following order Yb > Y ~ Dy > Sm in line with the relative Lewis acidity of the Ln(III) ion. Although the slow turnover of 2-Sm is additionally due to the poor solubility of the pre-catalyst in the reaction solvent. It is important to note that 1-Y and [Me3N•AlH3] do not catalyse this reaction under these conditions, therefore cooperativity between the two metal centres enables this transformation to occur at room temperature.