ArticleInorganic chemistry2023
Coordination of ε-Caprolactone to a Cationic Niobium(V) Alkoxide Complex: Fundamental Insight into Ring-Opening Polymerization via Coordination-Insertion.
Article in Inorganic chemistry, 2023. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 5 papers.
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Who cites it
5 citing papers in PubMed.
- Cyclic ester insertion into a bismuth-amide bond: isolable molecular models for ROP initiation.Chemical communications (Cambridge, England) · 2026Article
- Amine Tris(phenolate) Ligands as a Versatile Scaffold for Early and Late Transition Metals: Synthesis and Application.ACS omega · 2026Review
- Article
- Synthetic Polymers for Drug, Gene, and Vaccine Delivery.Polymer science & technology (Washington, D.C.) · 2025Review
- Unexpected Periodicity in Cationic Group 5 Initiators for the Ring-Opening Polymerization of Lactones.Inorganic chemistry · 2024Article
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Authors and funding
7 authors.
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Abstract
We report three niobium-based initiators for the catalytic ring-opening polymerization (ROP) of ε-caprolactone, exhibiting good activity and molecular weight control. In particular, we have prepared on the gram-scale and fully characterized a monometallic cationic alkoxo-Nb(V) ε-caprolactone adduct representing, to the best of our knowledge, an unprecedented example of a metal complex with an intact lactone monomer and a functional ROP-initiating group simultaneously coordinated at the metal center. At 80 °C, all three systems initiate the immortal solution-state ROP of ε-caprolactone via a coordination-insertion mechanism, which has been confirmed through experimental studies, and is supported by computational data. Natural bond orbital calculations further indicate that polymerization may necessitate isomerization about the metal center between the alkoxide chain and the coordinated monomer. The observations made in this work are expected to inform mechanistic understanding both of amine tris(phenolate)-supported metal alkoxide ROP initiators, including various highly stereoselective systems for the polymerization of lactides and of coordination-insertion-type ROP protocols more broadly.
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Registered trials
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