Heteroleptic zinc complexes containing side‐arm donor‐functionalized tridentate β‐ketoiminate ligands were obtained from metalation reactions of β‐ketoimines L1/2/3^Do1/2/3/4H [L1 = {(OC(Me)C(H)C(Me)NCH₂CH₂Do)}, L2 = {(OC(Me)C(H)C(Me)NCH₂CH₂CH₂Do)}, L3 = {(OC(OMe)C(H)C(Me)NCH₂CH₂Do)}; Do1 = NMe₂, Do2 = NEt₂; Do3 = Pyr, Do4 = OMe] with equimolar amounts of Zn[N(SiMe₃)₂]₂ [L1^Do1ZnN(SiMe₃)₂ (1), L1^Do2ZnN(SiMe₃)₂ (2)] and ZnEt₂ [L1^Do3ZnEt (3), L2^Do3ZnEt (4), L3^Do1ZnEt (5), L3^Do4ZnEt (6)]. Analogous reactions of AlMe₃ and Cp*MMe₃ with L1^Do1/2H yielded homoleptic aluminum [L1^Do1AlMe₂ (7), L1^Do2AlMe₂ (8), L2^Do1AlMe₂ (9)], titanium [L1^Do2Ti(Me₂)Cp* (10)] and zirconium complexes [L1^Do2Zr(Me₂)Cp* (11)]. In addition, 7 reacts with an ethereal HCl solution with methane elimination and formation of L1^Do1Al(Cl)Me (12) and L1^Do1AlCl₂ (13), whereas the reaction with one and two equivalents of 2,6‐dimethylphenol yielded L1^Do1Al(Me)O‐2,6‐Me₂C₆H₃ (14) and L1^Do1Al(O‐2,6‐Me₂C₆H₃)₂ (15). The complexes were characterized by elemental analysis, ¹H, ¹³C NMR, and IR spectroscopy and single‐crystal X‐ray analysis (2, 4, 7, 10, 12–14).

Dedicated to Professor Werner Uhl on the Occasion of his 65th Birthday