Pushing the upper limit of nucleophilicity scales by mesoionic N‐heterocyclic olefins

dc.contributor.authorEitzinger, Andreas
dc.contributor.authorReitz, Justus
dc.contributor.authorAntoni, Patrick W.
dc.contributor.authorMayr, Herbert
dc.contributor.authorOfial, Armin R.
dc.contributor.authorHansmann, Max M.
dc.date.accessioned2024-11-19T09:05:39Z
dc.date.available2024-11-19T09:05:39Z
dc.date.issued2023-08-04
dc.description.abstractA series of mesoionic, 1,2,3-triazole-derived N-heterocyclic olefins (mNHOs), which have an extraordinarily electron-rich exocyclic CC-double bond, was synthesized and spectroscopically characterized, in selected cases by X-ray crystallography. The kinetics of their reactions with arylidene malonates, ArCH=C(CO2Et)2, which gave zwitterionic adducts, were investigated photometrically in THF at 20 °C. The resulting second-order rate constants k2(20 °C) correlate linearly with the reported electrophilicity parameters E of the arylidene malonates (reference electrophiles), thus providing the nucleophile-specific N and sN parameters of the mNHOs according to the correlation lg k2(20 °C)=sN(N+E). With 21<N<32, the mNHOs are much stronger nucleophiles than conventional NHOs. Some mNHOs even excel the reactivity of mono- and diacceptor-substituted carbanions. It is exemplarily shown that the reactivity parameters thus obtained allow to calculate the rate constants for mNHO reactions with further Michael acceptors and predict the scope of reactions with other electrophilic reaction partners including carbon dioxide, which gives zwitterionic mNHO-carboxylates. The nucleophilicity parameters N correlate linearly with a linear combination of the quantum-chemically calculated methyl cation affinities and buried volumes of mNHOs, which offers a valuable tool to tailor the reactivities of strong carbon nucleophiles.en
dc.identifier.urihttp://hdl.handle.net/2003/42764
dc.identifier.urihttp://dx.doi.org/10.17877/DE290R-24596
dc.language.isoen
dc.relation.ispartofseriesAngewandte Chemie / International edition; 62(40)
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subjectDFT Calculationsen
dc.subjectKineticsen
dc.subjectMesoionic Compoundsen
dc.subjectMethyl Cation Affinitiesen
dc.subject.ddc540
dc.titlePushing the upper limit of nucleophilicity scales by mesoionic N‐heterocyclic olefinsen
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.primarycitationA. Eitzinger, J. Reitz, P. W. Antoni, H. Mayr, A. R. Ofial, M. M. Hansmann, Angew. Chem. Int. Ed. 2023, 62, e202309790.
eldorado.secondarypublication.primaryidentifierhttps://doi.org/10.1002/anie.202309790

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