A new, natural lysine-based (salen)CrIIICl ((lys-salen)CrIIICl) complex was prepared and its catalytic activity for the copolymerization of CO2 and cyclohexene oxide (CHO) was described in the presence of PPNCl (PPN+ = bis(triphenylphosphoranylidene)ammonium) as cocatalyst. The influence of the reaction time, operating temperature and the molar ratio of the catalyst components on the copolymerization was investigated in detail. The results showed that the (lys-salen)CrIIICl, synthesized from non-ortho-diamine, could effectively catalyze the alternating copolymerization (carbonate linkages = 94.6–99.0%). The selectivity was >95%, and was less sensitive to the temperature and the molar ratio of catalyst components, compared to that of the copolymerization catalyzed by traditional salen–metal complexes. The ESI-MS analyses of oligomer and (lys-salen)CrIIICl indicated that a possible chain-transfer reaction had taken place, which might be induced by the water coordinating to the central metal ion.
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