Synthesis and X-ray Crystal Structures of β-Ketoiminate Complexes

Heteroleptic zinc complexes containing side‐arm donor‐functionalized tridentate β‐ketoiminate ligands were obtained from metalation reactions of β‐ketoimines L1/2/3Do1/2/3/4H [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 [L1Do1ZnN(SiMe3)2 (1), L1Do2ZnN(SiMe3)2 (2)] and ZnEt2 [L1Do3ZnEt (3), L2Do3ZnEt (4), L3Do1ZnEt (5), L3Do4ZnEt (6)]. Analogous reactions of AlMe3 and Cp*MMe3 with L1Do1/2H yielded homoleptic aluminum [L1Do1AlMe2 (7), L1Do2AlMe2 (8), L2Do1AlMe2 (9)], titanium [L1Do2Ti(Me2)Cp* (10)] and zirconium complexes [L1Do2Zr(Me2)Cp* (11)]. In addition, 7 reacts with an ethereal HCl solution with methane elimination and formation of L1Do1Al(Cl)Me (12) and L1Do1AlCl2 (13), whereas the reaction with one and two equivalents of 2,6‐dimethylphenol yielded L1Do1Al(Me)O‐2,6‐Me2C6H3 (14) and L1Do1Al(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, 1214).

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


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