Lactide polymerization catalyzed by Mg and Zn diketiminate complexes with flexible ligand frameworks

Diketimine ligands bearing N-benzyl, N-9-anthrylmethyl and N-mesitylmethyl substituents (nacnac(Bn)H, nacnac(An)H, and nacnac(Mes)H) were prepared from condensation of the amine with either acetyl acetone or its ethylene glycol monoketal. Chlorination with N-chlorosuccinimide in the 3-position yielded Clnacnac(Bn)H and Clnacnac(An)H. The ligands were reacted with Zn(TMSA)(2) (TMSA = N(SiMe3)(2)) to yield nacnac(An)Zn( TMSA) and Clnacnac(Bn)Zn(TMSA). Protonation with isopropanol afforded nacnac(An)ZnOiPr and Clnacnac(Bn)ZnOiPr. Reaction of the diketimines with Mg(TMSA)(2) afforded nacnac(An)Mg(TMSA), nacnac(Mes)Mg( TMSA), Clnacnac(Bn)Mg(TMSA) and Clnacnac(An)Mg(TMSA). Subsequent protonation with tert-butanol produced nacnac(Mes)MgOtBu and Clnacnac(Bn)MgOtBu, but only decomposition was observed with N-anthrylmethyl substituents. Most complexes were characterized by X-ray diffraction studies. TMSA complexes were monomeric and alkoxide complexes dimeric in the solid state. All alkoxide complexes, as well as nacnac(An)Mg(TMSA)/BnOH and Clnacnac(An)Mg(TMSA)/BnOH were moderately to highly active in rac-lactide polymerization (90% conversion in 30 s to 3 h). nacnac(An)ZnOiPr produced highly heterotactic polymers (P-r = 0.90), Clnacnac(Bn)MgOtBu/BnOH produced slightly isotactic polymers at -30 degrees C (P-r = 0.43), and all other catalysts produced atactic polymers with a slight heterotactic bias.