Mononuclear and Multinuclear O^N^O‐donor Zn(II) Complexes as Robust Catalysts for the Production and Depolymerization of Poly(Lactide)

Mononuclear and multinuclear O^N^O‐donor Zn(II) complexes are herein reported as catalysts in the ring‐opening polymerization (ROP) of rac ‐lactide ( rac ‐LA) and depolymerization of poly(lactide) (PLA). Reactions of imino‐phenol proligand 2[((2‐hydroxyethyl)imino)methyl]phenol ( L1H 2 ) with ZnCl 2 and ZnEt 2 afforded the dinuclear and tetranuclear complexes [Zn 2 ( L1H ) 2 Cl 2 ] ( Zn1 ) and [Zn 4 ( L1 ) 4 ] ( Zn2 ), respectively. Separately, treatments of proligands 2‐[1‐((2‐hydroxyethyl)imino)ethyl]phenol ( L2H 2 ) and [((2‐methoxyethyl)imino)methyl]phenol ( L3H ) with ZnCl 2 gave the respective mononuclear complexes [Zn( L2H 2 ) 2 Cl 2 ] ( Zn3 ) and [Zn( L3H ) 2 Cl 2 ] ( Zn4 ), while the reactions of L3H with ZnEt 2 afforded the bis(chelated) mononuclear complex [Zn( L3 ) 2 ] ( Zn5 ). The complexes were characterized using NMR and IR spectroscopy, elemental analyses and single crystal X‐ray crystallography. All the Zn(II) complexes showed high catalytic activities in the ROP of rac ‐LA ( k app of up to 4.18 × 10 −4 s −1 ) to give moderate molecular weight PLA (39,960 g mol −1 ) with relatively narrow dispersities ( Đ = 1.4–2.1). The complexes produced mainly atactic PLAs with P r values of 0.51–0.58. More significantly, complexes Zn1 , Zn2 , and Zn5 were also active in the depolymerization of commercial PLA in methanol ( k app of up to 2.67 × 10 −4 s −1 ) to produce alkyl lactates. The ROP and depolymerization behavior were largely controlled by the structure and nuclearity of the complexes.