The salts Li[Al(C 4 H 8 N) 4 ]ؒnC 4 H 8 NH (n = 1, 2; C 4 H 8 NH = pyrrolidine) have been prepared and characterised in solution by 1 H-, 13 C-, 7 Li-and 27 Al-NMR spectroscopy. Their reaction with AlCl 3 (Cl/Li molar ratio = 3) affords the binary amido derivative [Al(C 4 H 8 N) 3 ] 2 , which, on turn, is reactive towards AlXAlternatively, the monochloro species Al(CH 3 ) 2 Cl-(C 4 H 8 NH) results from the reaction of Al(CH 3 ) 3 (C 4 H 8 NH) and AlCl 3 (C 4 H 8 NH) (CH 3 /Cl molar ratio = 2). The dichloro-methyl derivative Al(CH 3 )Cl 2 (C 4 H 8 NH) is obtained by reacting Al(CH 3 ) 3 (C 4 H 8 NH) and AlCl 3 (C 4 H 8 NH) (Cl/CH 3 molar ratio = 2). The Lewis adducts AlCl 3 (amine) n (amine = pyrrolidine, n = 1, 2; amine = N,N,NЈ-trimethylpropanediamine, n = 1) have been isolated when AlCl 3 was contacted with the stoichiometric amount of the amine. At variance with N,N,NЈ-trimethylpropanediamine, N,N,NЈ-trimethylethylenediamine and N,N,NЈ,NЈ-tetramethylethylenediamine react with AlCl 3 yielding the salt derivatives [AlCl 2 (amine) 2 ][AlCl 4 ]. The dynamic processes of the coordinated amine ligands of AlCl 3 (amine) n (amine = pyrrolidine, n = 1, 2; amine = N,N,NЈ-trimethylpropanediamine, n = 1) and [AlCl 2 (amine) 2 ][AlCl 4 ] (amine = N,N,NЈ,NЈ-tetramethylethylenediamine) have been investigated in solution by NMR spectroscopy.