The N-imidoylamidine ligand i-Pr2C6H3N(C(Me)NC(6)H(3)i-Pr-2)(2) 2 was prepared. Direct reactions with AlI3 or AlMe3 afforded [(i-Pr2C6H3N(C(Me)NC(6)H(3)i-Pr-2)(2))AlI2][AlI4] 3 and [i-Pr2C6H3N(C(Me)NC(6)H(3)i-Pr-2)(2))AlMe2][AlMe4] (.) AlMe3 4, respectively. Thermolysis of 4 gave (i-Pr2C6H3NC(=CH2)(NC(6)H(3)i-Pr-2)(C(Me)NC(6)H(3)i-Pr-2)AlMe2 6. Subsequent reaction with B(C6F5) 3 gave the zwitterionic species [(i-Pr2C6H3)N(C(=CH2)NC(6)H(3)i-Pr-2)(C(Me)NC(6)H(3)iPr(2))AlMe(mu-MeB(C6F5)(3))] 7. In a related reactions of 2, [Ph3C][B(C6F5)(4)] andAlMe(3), AlH3 (.) NEtMe2 or AlD3 (.) NMe3, the complexes [(i-Pr2C6H3N(C(Me)NC(6)H(3)i-Pr-2)(2))AlR2][B(C6F5)(4)](R = Me 5, H 8, D 9) and [(i-Pr2C6H3)N(C(=CH2)NC(6)H(3)i-Pr-2)(C(Me)NC(6)H(3)i-Pr-2)AlH][B(C6F5)(4)] 10 are formed. Single-crystal X-ray data for 2, 3, 5 and 10 are reported.