Mesoionic N-heterocyclic olefins as initiators for the Lewis pair polymerization of epoxides

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dc.contributor.authorHaug, Iris
dc.contributor.authorReitz, Justus
dc.contributor.authorZiane, Célia
dc.contributor.authorBuchmeiser, Michael R.
dc.contributor.authorHansmann, Max M.
dc.contributor.authorNaumann, Stefan
dc.date.accessioned2025-04-25T13:45:41Z
dc.date.available2025-04-25T13:45:41Z
dc.date.issued2024-03-24
dc.description.abstractMesoionic N-heterocyclic olefins (mNHOs) have recently emerged as a novel class of highly nucleophilic and super-basic σ-donor compounds. Making use of these properties in synthetic polymer chemistry, it is shown that a combination of a specific mNHO and a Mg-based Lewis acid (magnesium bis(hexamethyldisilazide), Mg(HMDS)2) delivers poly(propylene oxide) in quantitative yields from the polymerization of the corresponding epoxide (0.1 mol% mNHO loading). The initiation mechanism involves monomer activation by the Lewis acid and direct ring-opening of the monomer by nucleophilic attack of the mNHO, forming a zwitterionic propagating species. Modulation of the mNHO properties is thereby a direct tool to impact initiation efficiency, revealing a sterically unencumbered triazole-derivative as particularly useful. The joint application of mNHOs together with borane-type Lewis acids is also outlined, resulting in high conversions and fast polymerization kinetics. Importantly, while molar mass distributions remain relatively broad, indicating faster propagation than initiation, the overall molar masses are significantly lower than found in the case of regular NHOs, underlining the increased nucleophilicity and ensuing improved initiation efficiency of mNHOs.en
dc.identifier.urihttp://hdl.handle.net/2003/43681
dc.identifier.urihttp://dx.doi.org/10.17877/DE290R-25454
dc.language.isoen
dc.relation.ispartofseriesMacromolecular rapid communications; 45(12)
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subjectboranesen
dc.subjectepoxidesen
dc.subjectmagnesiumen
dc.subjectorganocatalysisen
dc.subjectpolyethersen
dc.subject.ddc540
dc.titleMesoionic N-heterocyclic olefins as initiators for the Lewis pair polymerization of epoxidesen
dc.typeText
dc.type.publicationtypeResearchArticle
dcterms.accessRightsopen access
eldorado.openaire.projectidentifierinfo:eu-repo/grantAgreement/EC/HE/101077332/EU/NAME/CC-CHARGED
eldorado.secondarypublicationtrue
eldorado.secondarypublication.primarycitationI. Haug, J. Reitz, C. Ziane, M. R. Buchmeiser, M. M. Hansmann, S. Naumann, Mesoionic N-Heterocyclic Olefins as Initiators for the Lewis Pair Polymerization of Epoxides. Macromol. Rapid Commun. 2024, 45, 2300716. https://doi.org/10.1002/marc.202300716
eldorado.secondarypublication.primaryidentifierhttps://doi.org/10.1002/marc.202300716

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