Triplet vinylidenes based on (benz)imidazole and 1,2,3-triazole N-heterocycles

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dc.contributor.authorKutin, Yury
dc.contributor.authorReitz, Justus
dc.contributor.authorDrosou, Maria
dc.contributor.authorAntoni, Patrick W.
dc.contributor.authorHe, Yijie
dc.contributor.authorSelve, Victor R.
dc.contributor.authorBoschmann, Sergius
dc.contributor.authorSavitsky, Anton
dc.contributor.authorPantazis, Dimitrios A.
dc.contributor.authorKasanmascheff, Müge
dc.contributor.authorHansmann, Max M.
dc.date.accessioned2025-08-19T08:10:56Z
dc.date.available2025-08-19T08:10:56Z
dc.date.issued2025-06-05
dc.description.abstractTriplet vinylidenes, a new class of carbon-centered diradicals containing a monosubstituted carbon atom, remain largely unexplored. A series of triplet vinylidenes based on five-membered heterocycles, featuring 2- and 4-imidazole, benzimidazole as well as 1,2,3-triazole backbones, are generated upon irradiation of stable diazoalkenes and are investigated by electron paramagnetic resonance (EPR) spectroscopy. While the calculated S/T gaps strongly vary (∼9.9–18.4 kcal/mol), the experimental zero-field splitting (ZFS) D values are positioned in a rather narrow and characteristic range of D ∼ 0.366–0.399 cm–1. Electron nuclear double resonance (ENDOR) studies with 13C-labeled samples combined with quantum chemical calculations reveal a common motif of Aiso(13C) ≈ 50 MHz for the electronic structure of the vinylidene class. EPR decay experiments confirm that steric and electronic tuning of the heterocycle can hinder C–H activation pathways leading to the highest reported stabilities of up to 150 K. Quantum chemical studies elucidate and contrast plausible C–H insertion pathways, identifying an early triplet-to-singlet spin surface transition as the key factor that governs the stability of the vinylidenes.en
dc.identifier.urihttp://hdl.handle.net/2003/43817
dc.language.isoen
dc.relation.ispartofseriesJACS Au; 5(6)
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subjectvinylidenesen
dc.subjectreactive intermediatesen
dc.subjectEPR spectroscopyen
dc.subjectdiradicalsen
dc.subjectC–H activationen
dc.subject.ddc540
dc.titleTriplet vinylidenes based on (benz)imidazole and 1,2,3-triazole N-heterocyclesen
dc.typeText
dc.type.publicationtypeArticle
dcterms.accessRightsopen access
eldorado.doi.registerfalse
eldorado.openaire.projectidentifierinfo:eu-repo/grantAgreement/EC/HE/101077332/EU/NAME/CC-CHARGED
eldorado.secondarypublicationtrue
eldorado.secondarypublication.primarycitationKutin, Y., Reitz, J., Drosou, M., Antoni, P. W., He, Y., Selve, V. R., Boschmann, S., Savitsky, A., Pantazis, D. A., Kasan­mascheff, M., & Hansmann, M. M. (2025). Triplet vinylidenes based on (benz)imidazole and 1,2,3-triazole N-heterocycles. JACS Au, 5(6), 2884–2897. https://doi.org/10.1021/jacsau.5c00491
eldorado.secondarypublication.primaryidentifierhttps://doi.org/10.1021/jacsau.5c00491

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