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Herein, we report the tricyclic pnictogen radical cations [(ADC)E]\n 2<\/jats:sub>\n [B], [\n 2<\/jats:bold>\n \u2010E][B] (ADC\u00a0=\u00a0PhC{N(Dipp)C}\n 2<\/jats:sub>\n ; Dipp\u00a0=\u00a02,6\u2010\n i<\/jats:italic>\n Pr\n 2<\/jats:sub>\n C\n 6<\/jats:sub>\n H\n 3<\/jats:sub>\n ; E\u00a0=\u00a0P, As, Sb; [B] = [B1] = B(C\n 6<\/jats:sub>\n F\n 5<\/jats:sub>\n )\n 4<\/jats:sub>\n or [B2] = {3,5\u2010(CF\n 3<\/jats:sub>\n )\n 2<\/jats:sub>\n C\n 6<\/jats:sub>\n H\n 3<\/jats:sub>\n }) featuring a central 7\u03c0\u2010electron planar C\n 4<\/jats:sub>\n E\n 2<\/jats:sub>\n ring embedded between two 1,3\u2010imidazole\u2010based anionic dicarbene (ADC) frameworks, as crystalline solids. [\n 2<\/jats:bold>\n \u2010E][B] are prepared by one\u2010electron (1e) oxidations of the corresponding base\u2010stabilized cyclic bis\u2010pnictinidene compounds [(ADC)E]\n 2<\/jats:sub>\n (\n 1<\/jats:bold>\n \u2010E). Calculated spin densities (for E\u00a0=\u00a0P 76%, As 80%, Sb 88%) and EPR measurements suggest that [\n 2<\/jats:bold>\n \u2010E]\n \u25cf+<\/jats:sup>\n are pnictogen\u2010centered radicals and stabilized by the delocalization of the unpaired electron over the C\n 4<\/jats:sub>\n E\n 2<\/jats:sub>\n ring. The EPR spectra of [\n 2<\/jats:bold>\n \u2010E][B] exhibit characteristic signals for\n S<\/jats:italic>\n = \u00bd systems with clear hyperfine coupling constants for the two similar P, As, or Sb nuclei. Further 1e\u2010oxidations of [\n 2<\/jats:bold>\n \u2010E][B] result in the dicationic 6\u03c0\u2010electron C\n 4<\/jats:sub>\n E\n 2<\/jats:sub>\n \u2010species [(ADC)E]\n 2<\/jats:sub>\n [B]\n 2<\/jats:sub>\n [\n 3<\/jats:bold>\n \u2010E][B]\n 2<\/jats:sub>\n , which readily undergo comproportionations with\n 1<\/jats:bold>\n \u2010E to afford [\n 2<\/jats:bold>\n \u2010E][B]. The radical reactivity of [\n 2<\/jats:bold>\n \u2010E][B2] is shown with 2,2,6,6\u2010tetramethylpiperidinyloxyl (TEMPO) and diphenyl diselenide (PhSeSePh) in yielding compounds [(ADC)\n 2<\/jats:sub>\n E{E(TEMPO)}][B2] (\n 4<\/jats:bold>\n \u2010E) (E\u00a0=\u00a0P, Sb) and [(ADC)\n 2<\/jats:sub>\n P{P(SePh)}][B2] (\n 5<\/jats:bold>\n \u2010P), respectively.\n <\/jats:p>","DOI":"10.1002\/anie.202505142","type":"journal-article","created":{"date-parts":[[2025,3,31]],"date-time":"2025-03-31T03:59:50Z","timestamp":1743393590000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Annulated Radical Cations with a C\n 4<\/sub>\n E\n 2<\/sub>\n \u2010Core (E\u00a0=\u00a0P, As, Sb): Stable Pnictogen Analogs of Elusive Aryl Radical Anions of Birch Reduction Reactions"],"prefix":"10.1002","volume":"64","author":[{"given":"Henric","family":"Steffenfauseweh","sequence":"first","affiliation":[{"name":"Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry Center for Molecular Materials Faculty of Chemistry Universit\u00e4t Bielefeld Universit\u00e4tsstrasse 25 D\u201033615 Bielefeld Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yury V.","family":"Vishnevskiy","sequence":"additional","affiliation":[{"name":"Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry Center for Molecular Materials Faculty of Chemistry Universit\u00e4t Bielefeld Universit\u00e4tsstrasse 25 D\u201033615 Bielefeld Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Beate","family":"Neumann","sequence":"additional","affiliation":[{"name":"Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry Center for Molecular Materials Faculty of Chemistry Universit\u00e4t Bielefeld Universit\u00e4tsstrasse 25 D\u201033615 Bielefeld Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hans\u2010Georg","family":"Stammler","sequence":"additional","affiliation":[{"name":"Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry Center for Molecular Materials Faculty of Chemistry Universit\u00e4t Bielefeld Universit\u00e4tsstrasse 25 D\u201033615 Bielefeld Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Demi D.","family":"Snabili\u00e9","sequence":"additional","affiliation":[{"name":"University of Amsterdam (UvA), Faculty of Science, Van \u2019t Hoff Institute for Molecular Sciences (HIMS) Homogeneous and Supramolecular Catalysis Group Science Park 904 1098 XH Amsterdam The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bas","family":"de Bruin","sequence":"additional","affiliation":[{"name":"University of Amsterdam (UvA), Faculty of Science, Van \u2019t Hoff Institute for Molecular Sciences (HIMS) Homogeneous and Supramolecular Catalysis Group Science Park 904 1098 XH Amsterdam The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rajendra S.","family":"Ghadwal","sequence":"additional","affiliation":[{"name":"Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry Center for Molecular Materials Faculty of Chemistry Universit\u00e4t Bielefeld Universit\u00e4tsstrasse 25 D\u201033615 Bielefeld Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,5,19]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201900307"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-0037-1611887"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201801560"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/9781119613466.ch7"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CS00288D"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/cjoc.201700802"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/B978-0-12-801981-8.00006-X"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CS00739A"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar5003494"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3sc51174j"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/B978-0-08-097774-4.00116-9"},{"key":"e_1_2_8_12_1","volume-title":"Stable 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Numbers 2376455 (for [2\u2010P][B1]) 2376456 (for [2\u2010As][B1]) and 2376457 (for [2\u2010Sb][B2]) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."},{"key":"e_1_2_8_72_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja504001x"},{"key":"e_1_2_8_73_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC04701H"},{"key":"e_1_2_8_74_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja400219d"},{"key":"e_1_2_8_75_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201909144"},{"key":"e_1_2_8_76_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202400204"},{"key":"e_1_2_8_77_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201610334"},{"key":"e_1_2_8_78_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-017-02581-2"},{"key":"e_1_2_8_79_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202001739"},{"key":"e_1_2_8_80_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.2c00251"},{"key":"e_1_2_8_81_1","unstructured":"The EPR spectrum of [2\u2010Sb][B1] recorded at 298 K gave a very broad featureless and non\u2010interpretable signal."},{"key":"e_1_2_8_82_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202215244"},{"key":"e_1_2_8_83_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201801596"},{"key":"e_1_2_8_84_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8SC01209A"},{"key":"e_1_2_8_85_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201713346"},{"key":"e_1_2_8_86_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201804524"},{"key":"e_1_2_8_87_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201604682"},{"key":"e_1_2_8_88_1","doi-asserted-by":"publisher","DOI":"10.1002\/advs.202305545"},{"key":"e_1_2_8_89_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c12127"},{"key":"e_1_2_8_90_1","doi-asserted-by":"publisher","DOI":"10.1039\/D4SC06782G"},{"key":"e_1_2_8_91_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202207415"},{"key":"e_1_2_8_92_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1DT01624E"},{"key":"e_1_2_8_93_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19851180618"},{"key":"e_1_2_8_94_1","doi-asserted-by":"publisher","DOI":"10.1002\/mrc.1270090210"},{"key":"e_1_2_8_95_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2DT01093C"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202505142","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,12,6]],"date-time":"2025-12-06T05:46:24Z","timestamp":1764999984000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202505142"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,5,19]]},"references-count":95,"journal-issue":{"issue":"25","published-print":{"date-parts":[[2025,6,17]]}},"alternative-id":["10.1002\/anie.202505142"],"URL":"https:\/\/doi.org\/10.1002\/anie.202505142","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,5,19]]},"assertion":[{"value":"2025-03-04","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-03-28","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-05-19","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202505142"}}