Perfluoroaryl Zinc Catalysts Active in Cyclohexene Oxide Homopolymerization and Alternating Copolymerization with Carbon Dioxide

The zinc complex Zn(C6F5)(2)(toluene) (1) behaves as a very active and selective catalyst in cyclohexene oxide (CHO) polymerization to produce poly(cyclohexene oxide) (PCHO) by the trans-ring-opening of CHO with remarkable TOF values at room temperature. The ring-opening copolymerization (ROCOP) of CO2 with CHO catalysed by 1 yields poly(cyclohexene carbonate) (PCHC) when using benzyl alcohol (BnOH) as an initiator at 120 degrees C. The H-1 NMR monitoring of the in situ reaction of 1 with BnOH highlighted the formation of the dinuclear species [(C6F5)(2)Zn-2(BnO)(2)] (2) that was isolated and found an active catalyst in the ROCOP of CO2 with CHO in the absence of initiators. Interestingly, PCHCs by 2 in solventless conditions show polydispersity index (M-w/M-n) values close to 2, corresponding to those expected for a single-site catalyst; on the contrary, a broader polydispersity index of the polymer products was found in toluene solution, suggesting the formation of new zinc catalysts during the polymerization reaction.