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 L1/2/3 Do1/2/3/4 H [L1 = {(OC(Me)C(H)C(Me)NCH 2 CH 2 Do)}, L2 = {(OC(Me)C(H)C(Me)NCH 2 CH 2 CH 2 Do)}, L3 = {(OC(OMe)C(H)C(Me)NCH 2 CH 2 Do)}; Do1 = NMe 2 , Do2 = NEt 2 ; Do3 = Pyr, Do4 = OMe] with equimolar amounts of Zn[N(SiMe 3 ) 2 ] 2 [L1 Do1 ZnN(SiMe 3 ) 2 ( 1 ), L1 Do2 ZnN(SiMe 3 ) 2 ( 2 )] and ZnEt 2 [L1 Do3 ZnEt ( 3 ), L2 Do3 ZnEt ( 4 ), L3 Do1 ZnEt ( 5 ), L3 Do4 ZnEt ( 6 )]. Analogous reactions of AlMe 3 and Cp*MMe 3 with L1 Do1/2 H yielded homoleptic aluminum [L1 Do1 AlMe 2 ( 7 ), L1 Do2 AlMe 2 ( 8 ), L2 Do1 AlMe 2 ( 9 )], titanium [L1 Do2 Ti(Me 2 )Cp* ( 10 )] and zirconium complexes [L1 Do2 Zr(Me 2 )Cp* ( 11 )]. In addition, 7 reacts with an ethereal HCl solution with methane elimination and formation of L1 Do1 Al(Cl)Me ( 12 ) and L1 Do1 AlCl 2 ( 13 ), whereas the reaction with one and two equivalents of 2,6‐dimethylphenol yielded L1 Do1 Al(Me)O‐2,6‐Me 2 C 6 H 3 ( 14 ) and L1 Do1 Al(O‐2,6‐Me 2 C 6 H 3 ) 2 ( 15 ). The complexes were characterized by elemental analysis, 1 H, 13 C NMR, and IR spectroscopy and single‐crystal X‐ray analysis ( 2 , 4 , 7 , 10 , 12 – 14 ).