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The synthesis and characterization of a series of chiralzinc complexes(L1a–m)ZnN(SiMe3)2(2a–m) with C1-symmetric amido-oxazolinateligands (HL1a–m= 2-(2′-R1NH)phenyl-4-R2-oxazoline)have been described. Single-crystal X-ray crystallographic studiesconfirm that 2a(R1= 2,6-dimethylphenyl,R2= (S)-iPr) and 2d(R1= 2,6-dimethylphenyl, R2= (R)-iBu) arethree-coordinate, mononuclear complexes, and 2k(R1= PhCO, R2= (S)-iPr) exists as an amide oxygen-bridged dimer in thesolid state with zinc in a distorted tetrahedral geometry. These complexesare viable initiators for alternating copolymerization of carbon dioxide(CO2) and cyclohexene oxide (CHO), yielding poly(cyclohexenecarbonate) (PCHC) with good to high carbonate linkage and moderatemolecular weights and PDI values, depending on the substituents. ThePCHCs produced are typically isotactic, containing up to 72% m-centered tetrads by 2h(R1= 2,6-diisopropylphenyl,R2= (R)-iBu), and a rare case of syndiotactic PCHC (57% r-centered tetrads) is obtained with 2j(R1= (R)-1-(1-naphthyl)ethyl), R2= (R)-iBu). The asymmetric inductionis generally low, with up to 71% SSunit in the mainchain of the produced PCHCs. [ABSTRACT FROM AUTHOR]