Synthetic, structural and catalysis studies of Ni(II) and Cu(II) complexes of a series of phenoxy-ketimine ligands with controlled variations of sterics, namely 2-[1-(2,6-diethylphenylimino)ethyl]phenol ( 1a), 2-[1-(2,6-dimethylphenylimino)ethyl]phenol ( 1b) and 2-[1-(2-methylphenylimino)ethyl]phenol ( 1c), are reported. Specifically, the ligands 1a, 1b and 1c were synthesized by the TiCl 4 mediated condensation reactions of the respective anilines with o-hydroxyacetophenone in 21–23% yield. The nickel complexes, {2-[1-(2,6-diethylphenylimino)ethyl]phenoxy} 2Ni(II) ( 2a) and {2-[1-(2,6-dimethylphenylimino)ethyl]phenoxy} 2Ni(II) ( 2b), were synthesized by the reaction of the respective ligands 1a and 1b with Ni(OAc) 2 · 4H 2O in the presence of NEt 3 as a base in 71–75% yield. The copper complexes, {2-[1-(2,6-diethylphenylimino)ethyl]phenoxy} 2Cu(II) ( 3a), {2-[1-(2,6-dimethylphenylimino)ethyl]phenoxy} 2Cu(II) ( 3b) and {2-[1-(2-methylphenylimino)ethyl]phenoxy} 2Cu(II) ( 3c) were synthesized analogously by the reactions of the ligands 1a, 1b and 1c with Cu(OAc) 2 · H 2O in 70–87% yield. The molecular structures of the nickel and copper complexes 2a, 2b, 3a, 3b and 3c have been determined by X-ray diffraction studies. Structural comparisons revealed that the nickel centers in 2a and 2b are in square planar geometries while the geometry around the copper varied from being square planar in 3a and 3c to distorted square planar in 3b. The catalysis studies revealed that while the copper complexes 3a, 3b and 3c efficiently catalyze ring-opening polymerization (ROP) of l-lactide at elevated temperatures under solvent-free melt conditions, producing polylactide polymers of moderate molecular weights with narrow molecular weight distributions, the nickel counterparts 2a and 2b failed to yield the polylactide polymer.
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