Herein, we present the synthesis of three new neutral aryl-BIAN ZnCl2 complexes (where aryl-BIAN = bis(aryl-imino)acenaphthene) with formulations [Zn(4-iPrC6H4-BIAN)Cl2] (1), [Zn(2-iPrC6H4-BIAN)Cl2] (2) and [Zn(4-NO2C6H4-BIAN)Cl2] (3) obtained through a green synthesis methodology. Compounds 1 and 2 were fully characterized by elemental analysis, ESI-LS mass spectrometry, FT-IR ATR mode, and multinuclear NMR spectroscopic techniques. Compound 3 was characterized by elemental analysis, ESI-LS mass spectrometry and FT-IR, ATR mode. The solid-state molecular structures of compounds 1 and 2 were determined by single crystal X-ray diffraction. The new complexes 1, 2 and 3, and the known complexes of formulations [Zn(2,6-iPr2C6H3-BIAN)Cl2] (4) and [Zn(2,4,6-Me3C6H2-BIAN)Cl2] (5) were tested as catalysts in the cycloaddition reaction of CO2 and epoxides using the tetrabutylammonium bromide salt as a co-catalyst. Primary studies revealed that complex 4 presented the highest catalytic activity among all synthetized complexes. Good reaction TOFs were obtained for the conversion of propylene oxide (112 h−1) after 3 hours and for the conversion of styrene oxide (23 h−1) after 8 hours, at 4 MPa and 333 K. For more sterically hindered cyclohexene oxide, no cyclic carbonate formation was observed, under the same operational conditions. Furthermore, the effect of reaction time (1-40 h), pressure (0.5-40 MPa) and nucleophile to metal ratio (0.5-100) on final cyclic carbonate formation was investigated.