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Updated: Mar 10, 2026

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
Published on: December 16, 2022
Mechanistic Insights into the Carbon Dioxide/Cyclohexene Oxide Copolymerization Reaction: Is One Metal Center Enough?
Joan González-Fabra1, Fernando Castro-Gómez1, Arjan W Kleij1,2
1Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
Abstract:
A detailed study on the mechanism for the alternating copolymerization of cyclohexene oxide (CHO) and CO2 mediated by an [Al{amino-tri(phenolate)}]/NBu4 I binary catalyst system was performed by using DFT-based methods. Four potential mechanisms (one monometallic and three bimetallic) were considered for the first propagation cycle of the CHO/CO2 copolymerization. The obtained Gibbs free energies provided a rationale for the relative high activity of a non-covalent dimeric structure formed in situ and thus for the feasibility of a bimetallic mechanism to obtain polycarbonates quantitatively. Gibbs free energies also indicated that the alternating copolymerization was favored over the cyclic carbonate formation.
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