Cyclic Polyester Formation with an [OSSO]‐Type Iron(III) Catalyst
Abstract
The efficient formation of cyclic polyesters from the ring‐opening polymerization of lactide, ϵ‐caprolactone, and β‐butyrolactone catalyzed by a 1,4‐dithiabutanedyl‐2,2′‐bis(4,6‐dicumylphenol) [OSSO]‐FeCl complex activated with cyclohexene oxide was achieved. The catalyst was very active (initial turnover frequency up to 2718 h−1), robust, and worked with a monomer/Fe ratio up to 10 000. The formation of cyclic polymers was supported by using high‐resolution matrix‐assisted laser desorption ionization (MALDI) MS, and the average ring size (≈5 kDa for cyclic polylactide) independent of the reaction conditions. A monometallic ring‐opening polymerization/cyclization mechanism was proposed from the results of a kinetic investigation.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
Many iron catalyst studies were performed in solution, sometimes using the toxic propylene oxide as solvent and precursor to the initiating species.
“Many of these studies were performed in solution, sometimes using the toxic propylene oxide as solvent and precursor to the initiating species.”
Cites
Sustainable polymers from renewable resources
Zhu, Y., Romain, C., & Williams, C. K. (2016) · Nature · doi:10.1038/nature21001 · Cited by 2,762 · see citing works
Controlled Ring-Opening Polymerization of Lactide and Glycolide
Dechy-Cabaret, O., Martin-Vaca, B., & Bourissou, D. (2004) · Chemical Reviews · doi:10.1021/cr040002s · Cited by 2,257 · see citing works
An "Endless" Route to Cyclic Polymers
Bielawski, C. W., Benítez, D., & Grubbs, R. H. (2002) · Science · doi:10.1126/science.1075401 · Cited by 643 · see citing works
Ring-opening copolymerization (ROCOP): synthesis and properties of polyesters and polycarbonates
Paul, S., Zhu, Y., Romain, C., Brooks, R., Saini, P. K., & Williams, C. K. (2015) · Chemical Communications · doi:10.1039/c4cc10113h · Cited by 593 · see citing works
Synthetic approaches for the preparation of cyclic polymers
Laurent, B. A., & Grayson, S. M. (2009) · Chemical Society Reviews · doi:10.1039/b809916m · Cited by 488 · see citing works
Stereoselective Epoxide Polymerization and Copolymerization
Childers, M. I., Longo, J. M., Van Zee, N. J., LaPointe, A. M., & Coates, G. W. (2014) · Chemical Reviews · doi:10.1021/cr400725x · Cited by 471 · see citing works
Cyclic polymers: Synthetic strategies and physical properties
Kricheldorf, H. R. (2009) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.23755 · Cited by 430 · see citing works
O'Keefe, B. J., Breyfogle, L. E., Hillmyer, M. A., & Tolman, W. B. (2002) · Journal of the American Chemical Society · doi:10.1021/ja012689t · Cited by 297 · see citing works
Topological polymer chemistry: a cyclic approach toward novel polymer properties and functions
Yamamoto, T., & Tezuka, Y. (2011) · Polymer Chemistry · doi:10.1039/c1py00088h · Cited by 272 · see citing works
Zwitterionic Ring-Opening Polymerization for the Synthesis of High Molecular Weight Cyclic Polymers
Brown, H. A., & Waymouth, R. M. (2013) · Accounts of Chemical Research · doi:10.1021/ar400072z · Cited by 255 · see citing works
Nasongkla, N., Chen, B., Macaraeg, N., Fox, M. E., Fréchet, J. M. J., & Szoka, F. C. (2009) · Journal of the American Chemical Society · doi:10.1021/ja900062u · Cited by 240 · see citing works
Ring-opening polymerization by lithium catalysts: an overview
Sutar, A. K., Maharana, T., Dutta, S., Chen, C., & Lin, C. (2009) · Chemical Society Reviews · doi:10.1039/b912806a · Cited by 221 · see citing works
Biernesser, A. B., Li, B., & Byers, J. A. (2013) · Journal of the American Chemical Society · doi:10.1021/ja407920d · Cited by 220 · see citing works
Gallium and indium complexes for ring-opening polymerization of cyclic ethers, esters and carbonates
Dagorne, S., Normand, M., Kirillov, E., & Carpentier, J.-F. (2013) · Coordination Chemistry Reviews · doi:10.1016/j.ccr.2013.02.012 · Cited by 215 · see citing works
Rapid and Controlled Polymerization of Lactide by Structurally Characterized Ferric Alkoxides
O'Keefe, B. J., Monnier, S. M., Hillmyer, M. A., & Tolman, W. B. (2000) · Journal of the American Chemical Society · doi:10.1021/ja003537l · Cited by 207 · see citing works
Cyclic polyesters: synthetic approaches and potential applications
Hoskins, J. N., & Grayson, S. M. (2010) · Polymer Chemistry · doi:10.1039/c0py00102c · Cited by 166 · see citing works
Kernbichl, S., Reiter, M., Adams, F., Vagin, S. I., & Rieger, B. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.7b01295 · Cited by 166 · see citing works
Chen, B., Jerger, K., Fréchet, J. M. J., & Szoka, F. C. (2009) · Journal of Controlled Release · doi:10.1016/j.jconrel.2009.05.021 · Cited by 163 · see citing works
Recent progress on the synthesis of cyclic polymers via ring‐expansion strategies
Chang, Y. A., & Waymouth, R. M. (2017) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.28635 · Cited by 157 · see citing works
Kricheldorf, H. R., & Lee, S. (1995) · Macromolecules · doi:10.1021/ma00124a004 · Cited by 139 · see citing works
Monica, F. D., Maity, B., Pehl, T. M., Buonerba, A., Nisi, A. D., Monari, M., Grassi, A., Rieger, B., Cavallo, L., & Capacchione, C. (2018) · ACS Catalysis · doi:10.1021/acscatal.8b01695 · Cited by 139 · see citing works
Self-citationA well-defined iron(ii) alkoxide initiator for the controlled polymerisation of lactide
Gibson, V. C., Marshall, E. L., Navarro-Llobet, D., White, A. J. P., & Williams, D. J. (2002) · Journal of the Chemical Society Dalton Transactions · doi:10.1039/b209703f · Cited by 111 · see citing works
A New Strategy for the Synthesis of Macrocycles. The Polyhomologation of Boracyclanes
Shea, K. J., Lee, S. Y., & Busch, B. B. (1998) · The Journal of Organic Chemistry · doi:10.1021/jo981174q · Cited by 105 · see citing works
Homogeneous Iron Catalysts in the Reaction of Epoxides with Carbon Dioxide
Monica, F. D., Buonerba, A., & Capacchione, C. (2018) · Advanced Synthesis & Catalysis · doi:10.1002/adsc.201801281 · Cited by 104 · see citing works
Self-citationRobert, C., Schmid, T. E., Richard, V., Haquette, P., Raman, S. K., Rager, M.-N., Gauvin, R. M., Morin, Y., Trivelli, X., Guérineau, V., et al. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.7b01749 · Cited by 101 · see citing works
Anionic iron(II) alkoxides as initiators for the controlled ring‐opening polymerization of lactide
McGuinness, D. S., Marshall, E. L., Gibson, V. C., & Steed, J. W. (2003) · Journal of Polymer Science Part A: Polymer Chemistry · doi:10.1002/pola.10946 · Cited by 96 · see citing works
Duan, R., Hu, C., Li, X., Pang, X., Sun, Z., Chen, X., & Wang, X. (2017) · Macromolecules · doi:10.1021/acs.macromol.7b01766 · Cited by 96 · see citing works
Tezuka, Y. (2012) · WORLD SCIENTIFIC eBooks · doi:10.1142/8443 · Cited by 93 · see citing works
Monica, F. D., Vummaleti, S. V. C., Buonerba, A., Nisi, A. D., Monari, M., Milione, S., Grassi, A., Cavallo, L., & Capacchione, C. (2016) · Advanced Synthesis & Catalysis · doi:10.1002/adsc.201600621 · Cited by 92 · see citing works
Self-citationCozzolino, M., Leo, V., Tedesco, C., Mazzeo, M., & Lamberti, M. (2018) · Dalton Transactions · doi:10.1039/c8dt03169j · Cited by 83 · see citing works
Castro‐Osma, J. A., Alonso‐Moreno, C., García-Martínez, J. C., Fernández‐Baeza, J., Sánchez‐Barba, L. F., Lara‐Sánchez, A., & Otero, A. (2013) · Macromolecules · doi:10.1021/ma401216u · Cited by 82 · see citing works
Rittinghaus, R. D., Schäfer, P. M., Albrecht, P., Conrads, C., Hoffmann, A., Ksiazkiewicz, A. N., Bienemann, O., Pich, A., & Herres‐Pawlis, S. (2019) · ChemSusChem · doi:10.1002/cssc.201900481 · Cited by 82 · see citing works
Della Monica, F., Luciano, E., Roviello, G., Grassi, A., Milione, S., & Capacchione, C. (2014) · Macromolecules · doi:10.1021/ma5003358 · Cited by 74 · see citing works
Self-citationLactide Cyclopolymerization by an Alumatrane-Inspired Catalyst
Weil, J., Mathers, R. T., & Getzler, Y. D. Y. L. (2012) · Macromolecules · doi:10.1021/ma201960p · Cited by 61 · see citing works
[OSSO]‐Type Fe(III) Metallate as Single‐Component Catalyst for the CO 2 Cycloaddition to Epoxides
Monica, F. D., Buonerba, A., Paradiso, V., Milione, S., Grassi, A., & Capacchione, C. (2018) · Advanced Synthesis & Catalysis · doi:10.1002/adsc.201801240 · Cited by 60 · see citing works
Self-citationShaik, M., Peterson, J., & Du, G. (2018) · Macromolecules · doi:10.1021/acs.macromol.8b02096 · Cited by 45 · see citing works
Sin, L. T., Rahmat, A. R., & Rahman, W. A. W. A. (2012) · Elsevier eBooks · doi:10.1016/b978-1-4557-2834-3.00002-1 · Cited by 43 · see citing works
Manna, C. M., Kaplan, H. Z., Li, B., & Byers, J. A. (2014) · Polyhedron · doi:10.1016/j.poly.2014.07.002 · Cited by 42 · see citing works
Herber, U., Hegner, K., Wolters, D., Siris, R., Wrobel, K., Hoffmann, A., Lochenie, C., Weber, B., Kuckling, D., & Herres‐Pawlis, S. (2017) · European Journal of Inorganic Chemistry · doi:10.1002/ejic.201601345 · Cited by 41 · see citing works
Salen-iron complexes: Synthesis, characterization and their reactivity with lactide
Liang, Y., Duan, R.-L., Hu, C.-Y., Li, L.-L., Pang, X., Zhang, W.-X., & Chen, X.-S. (2018) · Chinese Journal of Polymer Science · doi:10.1007/s10118-018-2068-0 · Cited by 36 · see citing works
Reisberg, S. H., Hurley, H. J., Mathers, R. T., Tanski, J. M., & Getzler, Y. D. Y. L. (2013) · Macromolecules · doi:10.1021/ma400046x · Cited by 35 · see citing works
BIAN‐Fe(η6‐C6H6): Synthesis, characterization, and l‐lactide polymerization
Brown, L. A., Wekesa, F. S., Unruh, D. K., Findlater, M., & Long, B. K. (2017) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.28688 · Cited by 32 · see citing works
Precise Synthesis, Properties, and Structures of Cyclic Poly(ε-caprolactone)s
Li, X., Ryu, W., Kim, H., & Ree, M. (2018) · Polymers · doi:10.3390/polym10060577 · Cited by 30 · see citing works
IronIII Half Salen Catalysts for Atom Transfer Radical and Ring-Opening Polymerizations
Fazekas, E., Nichol, G. S., Garden, J. A., & Shaver, M. P. (2018) · ACS Omega · doi:10.1021/acsomega.8b02432 · Cited by 24 · see citing works
Cyclic versus linear polylactide: Straightforward access using a single catalyst
Hu, C., Louisy, E., Fontaine, G., & Bonnet, F. (2017) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.28699 · Cited by 22 · see citing works
Lapenta, R., De Simone, N. A., Buonerba, A., Talotta, C., Gaeta, C., Neri, P., Grassi, A., & Milione, S. (2018) · Catalysis Science & Technology · doi:10.1039/c7cy02537h · Cited by 16 · see citing works
Self-citation
Flagged first, then by citations
Cited by
Sorted by citations
The influence of the functional end groups on the properties of polylactide-based materials
Kost, B., Baśko, M., Bednarek, M., Socka, M., Kopka, B., Łapienis, G., Biela, T., Kubisa, P., & Brzeziński, M. (2022) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2022.101556 · Cited by 115 · see citing works
Macrocyclic polymers: Synthesis, purification, properties and applications
Ochs, J., Pagnacco, C. A., & Barroso‐Bujans, F. (2022) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2022.101606 · Cited by 51 · see citing works
Progress of Ring-Opening Polymerization of Cyclic Esters Catalyzed by Iron Compounds
Wang, Y., Wang, X., Zhang, W., & Sun, W. (2023) · Organometallics · doi:10.1021/acs.organomet.3c00028 · Cited by 46 · see citing works
Munzeiwa, W. A., Omondi, B. O., & Nyamori, V. O. (2024) · Polymer Bulletin · doi:10.1007/s00289-024-05149-5 · Cited by 36 · see citing works
[OSSO]-bisphenolate metal complexes: A powerful and versatile tool in polymerization catalysis
Paradiso, V., Capaccio, V., Lamparelli, D. H., & Capacchione, C. (2020) · Coordination Chemistry Reviews · doi:10.1016/j.ccr.2020.213644 · Cited by 34 · see citing works
Self-citationMonica, F. D., Paradiso, V., Grassi, A., Milione, S., Cavallo, L., & Capacchione, C. (2020) · Chemistry - A European Journal · doi:10.1002/chem.201905455 · Cited by 22 · see citing works
Self-citationBruckmoser, J., Henschel, D., Vagin, S. I., & Rieger, B. (2022) · Catalysis Science & Technology · doi:10.1039/d2cy00436d · Cited by 20 · see citing works
Recent Advances in RO(CO)P of Bio-Based Monomers
Santoro, O., Izzo, L., & Monica, F. D. (2022) · Sustainable Chemistry · doi:10.3390/suschem3020017 · Cited by 20 · see citing works
Wang, H., & Ma, H. (2024) · Macromolecules · doi:10.1021/acs.macromol.4c00937 · Cited by 15 · see citing works
Suo, H., Liu, S., Liu, J., Zhang, Z., Qu, R., Gu, Y., & Qin, Y. (2023) · Polymer Chemistry · doi:10.1039/d3py00890h · Cited by 14 · see citing works
Santulli, F., Bruno, F., Mazzeo, M., & Lamberti, M. (2023) · ChemCatChem · doi:10.1002/cctc.202300498 · Cited by 15 · see citing works
Chen, J., Wu, X., Zhang, L., Duan, Z., & Liu, B. (2022) · Polymer Chemistry · doi:10.1039/d2py00115b · Cited by 12 · see citing works
Conrads, C., Burkart, L., Soerensen, S., Noichl, S., Kara, Y., Heck, J., Hoffmann, A., & Herres‐Pawlis, S. (2023) · Catalysis Science & Technology · doi:10.1039/d3cy01117h · Cited by 12 · see citing works
Niknam, F., Buonerba, A., Grassi, A., & Capacchione, C. (2024) · ChemCatChem · doi:10.1002/cctc.202400011 · Cited by 10 · see citing works
Self-citationFeng, R., Jie, S., Braunstein, P., & Li, B. (2020) · Macromolecular Chemistry and Physics · doi:10.1002/macp.202000075 · Cited by 9 · see citing works
Hashmi, O. H., Capet, F., Visseaux, M., & Champouret, Y. (2022) · European Journal of Inorganic Chemistry · doi:10.1002/ejic.202200073 · Cited by 9 · see citing works
[OSSO]‐Type Chromium(III) Complexes for the Reaction of CO2 with Epoxides
Niknam, F., Capaccio, V., Kleybolte, M. M., Lamparelli, D. H., Winnacker, M., Fiorani, G., & Capacchione, C. (2022) · ChemPlusChem · doi:10.1002/cplu.202200038 · Cited by 8 · see citing works
Self-citationGroup IV complexes with nitrogen based ligands in the ring opening polymerization of cyclic esters
Impemba, S., & Milione, S. (2024) · Inorganica Chimica Acta · doi:10.1016/j.ica.2024.122067 · Cited by 8 · see citing works
Self-citationRuiz‐Martínez, C., Pérez, J. M., Campos, F. M. A., Batuecas, M. T., Ortuño, M. Á., & Fernández, I. (2021) · Polymer Chemistry · doi:10.1039/d1py00547b · Cited by 8 · see citing works
Wang, Y., Zhang, W., Wang, X., Zuo, W., Xue, X., Ma, Y., & Sun, W. (2023) · RSC Advances · doi:10.1039/d3ra05867k · Cited by 7 · see citing works
Kirchhecker, S., Nguyen, N., Reichert, S., Lützow, K., Eselem Bungu, P. S., Jacobi von Wangelin, A., Sandl, S., & Neffe, A. T. (2023) · RSC Advances · doi:10.1039/d3ra03112h · Cited by 6 · see citing works
Stereoregular cyclic poly(3-hydroxybutyrate) enabled by catalyst-controlled tacticity and topology
Parker, C. R., Zhang, Z., Quinn, E. C., Reilly, L. T., & Chen, E. Y. ‐. (2025) · Polymer Chemistry · doi:10.1039/d4py01304b · Cited by 6 · see citing works
Zhang, Z., Zhou, Y., Liu, S., Li, B., Qu, R., Gu, Y., Suo, H., & Qin, Y. (2024) · Polymer Chemistry · doi:10.1039/d4py01034e · Cited by 4 · see citing works
Functional Polylactides Achieved by Iron‐Catalyzed (Co)Polymerization of Different Lactides
Zhu, P., Zhang, S., Zhang, W., Yu, X., Ma, Y., Zheng, T., & Sun, W. (2025) · ChemCatChem · doi:10.1002/cctc.202500083 · Cited by 4 · see citing works
Yu, B., Xu, X., Huang, Z.-N., Tao, K., Sun, H., Yang, Q., & Wang, W. (2023) · Organometallics · doi:10.1021/acs.organomet.2c00618 · Cited by 3 · see citing works
Cyclic Polyesters: Synthetic Methods and Perspectives
Huo, Z., Xie, X., & Tong, R. (2025) · Chemistry - An Asian Journal · doi:10.1002/asia.202500983 · Cited by 2 · see citing works
Recent Progress on the Synthesis of Cyclic Polymers
Curole, B. J., Miles, A. V., & Grayson, S. M. (2022) · Springer eBooks · doi:10.1007/978-981-16-6807-4_14 · Cited by 2 · see citing works
Wang, Y., Wang, C., & Ma, H. (2025) · 化学学报 · doi:10.6023/a24090275 · Cited by 2 · see citing works
Impemba, S., Viceconte, A., Tozio, I., Anwar, S., Manca, G., & Milione, S. (2024) · Polymers · doi:10.3390/polym16213047 · Cited by 1 · see citing works
Self-citationChen, L., Tai, L., Wang, X., Lin, F., Wu, Y., Wang, S., & Song, L. (2023) · Polymer Science Series B · doi:10.1134/s1560090423701245
Sohail, S., Yuan, R., Mahmood, Q., Ma, Y., Zhang, S., Zhang, W., & Sun, W. (2026) · Polymer science & technology. · doi:10.1021/polymscitech.6c00015
Esposito, S., D’Amato, A., Buonerba, A., Balzano, V., Giannini, L., Guerra, S., Tadiello, L., Blal, N., Guarnieri, D., & Capacchione, C. (2026) · ACS Sustainable Chemistry & Engineering · doi:10.1021/acssuschemeng.6c08419
Self-citation
- Authors
- Impemba, S., Della Monica, F., Grassi, A., Capacchione, C., & Milione, S.
- Affiliations
- University of Salerno (IT)
- Dipartimento di Chimica e Biologia “Adolfo Zambelli” Università degli Studi di Salerno Via Giovanni Paolo II, 132- 84084 Fisciano (SA) Italy
- Corresponding author
- Capacchione, Carmine
- Venue
- ChemSusChem
- Publisher
- Wiley
- Published
- 2019-10-23
- Volume
- 13
- Issue
- 1
- Pages
- 141-145
- ISSN
- 1864-5631 (ISSN-L)
- 1864-564X
- OpenAlex
- W2975191762
- Cited by
- 32
- References
- 46
- Citations by year
- 2026: 2 · 2025: 4 · 2024: 6 · 2023: 8 · 2022: 8 · 2021: 1 · 2020: 3
- FWCI
- 0.85
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- ChemSusChem (publishedVersion)
- PubMed (publishedVersion)
- IrInSubria (University of Insubria) (submittedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Keywords
- cyclic polyesters, ring-opening polymerization, iron(III) catalyst, lactide, ε-caprolactone, β-butyrolactone, catalyst robustness, turnover frequency, ring size distribution, polymerization mechanism, kinetic analysis
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review