Ammonia borane, NH ₃ BH ₃ (AB), is very attractive for hydrogen storage; however, it dehydrogenates exothermally, producing a mixture of polymeric products with limited potential for direct rehydrogenation. Recently, it was shown that AB complexed with Al ³⁺ in Al(BH ₄ ) ₃ ·AB endothermically dehydrogenates to a single product identified as Al(BH ₄ ) ₃ ·NHBH, with the potential for direct rehydrogenation of AB. Here we explore the reactivity of AB-derived RNH ₂ BH ₃ (R = ?CH ₃ , ?CH ₂ ?) with AlX ₃ salts (X = BH ₄ ^- , Cl ^- ), aiming to extend the series to different anions and to enlarge the stability window for Al(BH ₄ ) ₃ ·NRBH. Three novel complexes were identified: Al(BH ₄ ) ₃ ·CH ₃ NH ₂ BH ₃ having a molecular structure similar to that of Al(BH ₄ ) ₃ ·AB but different dehydrogenation properties, as well as [Al(CH ₃ NH ₂ BH ₃ ) ₂ Cl ₂ ][AlCl ₄ ] and [Al(NH ₂ CH ₂ CH ₂ NH ₂ )(BH ₄ ) ₂ ][Al(BH ₄ ) ₄ ], rare examples of Al ³⁺ making part of the cations and anions simultaneously. The latter compounds are of interest in the design of novel electrolytes for Al-based batteries. The coordination of two ABs to a single Al atom opens a route to materials with higher hydrogen content.