Heterolepic β‐Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide

Zinc phenoxide complexes L(1)ZnOAr 1–4 (L(1)=Me(2)NC(2)H(4)NC(Me)CHC(Me)O) and L(2)ZnOAr 5–8 (L(2)=Me(2)NC(3)H(6)NC(Me)CHC(Me)O) with donor‐functionalized β‐ketoiminate ligands (L(1/2)) and OAr substituents (Ar=Ph 1, 5; 2,6‐Me(2)‐C(6)H(3) 2, 6; 3,5‐Me(2)‐C(6)H(3) 3, 7; 4‐Bu‐C(6)H(4) 4, 8) with tuneable electronic and steric properties were synthesized and characterized. 1–8 adopt binuclear structures in the solid state except for 5, while they are monomeric in CDCl(3) solution. 1–8 are active catalysts for the ring opening polymerization (ROP) of lactide (LA) in CH(2)Cl(2) at ambient temperature and the catalytic activity is controlled by the electronic and steric properties of the OAr substituent, yielding polymers with high average molecular weight (M (n)) and moderately controlled molecular weight distribution (MWDs). 1 and 5 showed a living polymerization character and kinetic studies on the ROP of L–LA with 1 and 5 proved first order dependencies on the monomer concentration. Homonuclear decoupled (1)H‐NMR analyses of polylactic acid (PLA) formed with rac‐LA proved isotactic enrichment of the PLA microstructure.