Dinuclear Ce(IV) Aryloxides: Highly Active Catalysts for Anhydride/Epoxide Ring-Opening Copolymerization

Steven J. Gray, Karen Brown, Francis Y. T. Lam, Jennifer A. Garden, Polly L. Arnold

Research output: Contribution to journalArticlepeer-review


A library of new dinuclear CeIV complexes of the type [NEt4]2[Ce2X6(TP)(sol)2] (X = Cl, ODipp, OSiMe3; sol = py, THF), where TP represents a family of tetraphenolate ligands that control intermetallic distance, are readily made in good yields. The ligands strongly stabilize the cerium +4 oxidation state and allow the incorporation of alkylammonium cocations in an “ate” complex formulation that enables them to be used as soluble, single-component catalysts for the ring-opening copolymerization (ROCOP) of a variety of anhydrides and epoxides. High turnover frequencies (TOFs) are achieved with high ester linkage selectivity, low dispersities, and rates that are highly tunable by the intermetallic distance enforced by the TP ligand, demonstrating that a closely coupled di-CeIV unit provides excellent rates of ROCOP catalysis and that, more generally, rare-earth complexes deserve further attention as ROCOP initiators.
Original languageEnglish
Pages (from-to)948-958
Issue number7
Early online date25 Mar 2021
Publication statusE-pub ahead of print - 25 Mar 2021


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