Zinc Complexes of Piperazinyl‐Derived Aminephenolate Ligands: Synthesis, Characterization and Ring–Opening Polymerization Activity

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A series of zinc complexes was prepared from 4,6‐disubstituted (R,R′) o‐[(4‐methyl‐1‐piperazinyl)methyl]phenols ([ONNR′,R]H) and characterized by elemental analysis, 1H and 13C{1H} NMR spectroscopy, and X‐ray crystallography. Reaction of these products with diethylzinc gave Zn[ONNtBu,tBu]2 (1) as a monometallic complex and {[μ‐ONNR′,R]ZnEt}2 [R′ = Me, R = tBu, (2); R′ = R = tBu (3); R′ = R = tAm (4)] bimetallic species that have distorted tetrahedral environments about the Zn centres. Reaction of 3 and 4 with alcohols gave {[ONNtAm,tAm]Zn(μ‐OR″)}2 [R″ = Bn (5); R″ = Et (6)] bimetallic species in which the Zn centres are bridged by benzyl alkoxide and ethoxide groups, respectively. A morpholinyl derived ligand was also synthesized and characterized (L4H), and its 1:1 stoichiometric reaction with ZnEt2 resulted in complex 7, {[μ‐ONOtBu,tBu]ZnEt}2. The reactivity of complexes 2–7 in the ring‐opening polymerization of rac‐lactide (LA) and ϵ‐caprolactone (ϵ‐CL) was studied. Reactions of carbon dioxide with cyclohexene oxide in the presence of 6 or 7/ROH (R = Bn, Et) afforded cyclohexene carbonate.