Ph3PC – a monosubstituted C(0) atom in its triplet state

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dc.contributor.authorKutin, Yury
dc.contributor.authorKoike, Taichi
dc.contributor.authorDrosou, Maria
dc.contributor.authorSchnegg, Alexander
dc.contributor.authorPantazis, Dimitrios A.
dc.contributor.authorKasanmascheff, Müge
dc.contributor.authorHansmann, Max M.
dc.date.accessioned2025-04-25T14:18:26Z
dc.date.available2025-04-25T14:18:26Z
dc.date.issued2025-01-27
dc.description.abstractThis study introduces a novel class of carbon-centered diradicals: a monosubstituted C atom stabilized by a phosphine. The diradical Ph3P→C was photochemically generated from a diazophosphorus ylide precursor (Ph3PCN2) and characterized by EPR and isotope-sensitive ENDOR spectroscopy at low temperatures. Ph3P→C features an axial zero-field splitting parameter D=0.543 cm−1 with a vanishingly small rhombicity |E|/D=0.002. Time- and temperature-dependent measurements confirm a triplet ground state with a lifetime of approximately 10 min at 127 K in toluene-d8. Multireference electronic structure calculations predict a clear triplet ground state with a singlet-triplet gap greater than 20 kcal/mol. In contrast to divalent C(0) compounds, such as Ph3P→C←PPh3, in which carbon needs excitation into a highly-excited closed-shell 2s02p4 configuration, Ph3P→C can be explained by direct involvement of carbon in its natural 3P state arising from the 2s22p2 configuration.en
dc.identifier.urihttp://hdl.handle.net/2003/43685
dc.identifier.urihttp://dx.doi.org/10.17877/DE290R-25458
dc.language.isoen
dc.relation.ispartofseriesAngewandte Chemie. International edition; 64(10)
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subjectreactive intermediatesen
dc.subjectcarbonen
dc.subjectEPR spectroscopyen
dc.subjectdiradicalsen
dc.subjectcarbonesen
dc.subject.ddc540
dc.titlePh3PC – a monosubstituted C(0) atom in its triplet stateen
dc.typeText
dc.type.publicationtypeArticle
dcterms.accessRightsopen access
eldorado.openaire.projectidentifierinfo:eu-repo/grantAgreement/EC/HE/101077332/EU/NAME/CC-CHARGED
eldorado.secondarypublicationtrue
eldorado.secondarypublication.primarycitationY. Kutin, T. Koike, M. Drosou, A. Schnegg, D. A. Pantazis, M. Kasanmascheff, M. M. Hansmann, Angew. Chem. Int. Ed. 2025, 64, e202424166. https://doi.org/10.1002/anie.202424166
eldorado.secondarypublication.primaryidentifierhttps://doi.org/10.1002/anie.202424166

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