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Here, we show that visible\u2010light excitation unlocks new transition\u2010metal\u2010like reactivity in a well\u2010studied ONO\u2010pincer phosphine. Photochemical generation of \u03b1\u2010siloxy carbenes enables rapid P\u2500C bond formation, affording bicyclic phosphines with complete diastereocontrol. These phosphine intermediates readily engage with electrophiles to form air\u2010 and moisture\u2010stable phosphoranes, which, upon subsequent irradiation, undergo selective P\u2500C bond homolysis, releasing carbon\u2010centered radicals while regenerating the initial phosphine framework. Time\u2010resolved EPR spectroscopy and DFT calculations reveal that geometric constraint is crucial for accessing both carbene\u2010insertion rearrangement and P\u2500C bond homolysis pathways not observed with conventional phosphines. Together, these findings establish a rare light\u2010driven phosphine \u2192 phosphorane \u2192phosphine (P(III) \u2192 P(V) \u2192 P(III)) reactivity loop and demonstrate how structural constraint enables main\u2010group centers to perform elementary steps analogous to transition metals.<\/jats:p>","DOI":"10.1002\/anie.9531020","type":"journal-article","created":{"date-parts":[[2026,5,14]],"date-time":"2026-05-14T15:20:43Z","timestamp":1778772043000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Visible\u2010Light Unlocked Carbene Insertion and Radical Release in a Structurally Constrained Pincer Phosphorus Compound"],"prefix":"10.1002","volume":"65","author":[{"given":"Avisek","family":"Ghosh","sequence":"first","affiliation":[{"name":"CNRS\/Universit\u00e9 De Toulouse Laboratoire H\u00e9t\u00e9rochimie Fondamentale Et Appliqu\u00e9e (LHFA, UMR5069)  Toulouse France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9259-9609","authenticated-orcid":false,"given":"Aqeel A.","family":"Hussein","sequence":"additional","affiliation":[{"name":"Department of Biology College of Science Al\u2010Qasim Green University  Al\u2010Qasim Iraq"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jing","family":"Liu","sequence":"additional","affiliation":[{"name":"Center of Basic Molecular Science (CBMS) Department of Chemistry Tsinghua University  Beijing P. 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acyl radicals are commonly reported to undergo decarbonylation this reactivity is highly dependent on the nature of the substituent. Rapid CO extrusion is typically associated with alkyl\u2010substituted acyl radicals. In contrast aryl acyl radicals are considerably less prone to decarbonylation as the formation of a phenyl radical is significantly less favorable than that of a stabilized alkyl radical To the best of our knowledge decarbonylation of aromatic acyl radicals has not been experimentally observed. Consistent with this behavior time\u2010resolved EPR (trEPR) measurements in our system reveal an acyl radical lifetime on the millisecond timescale which enables productive bimolecular reactivity. Under these conditions we propose that the acyl radical undergoes hydrogen atom abstraction from the tropyl radical dimer (7) leading to the formation of benzaldehyde. In agreement with this mechanism no products arising from decarbonylation were detected and no direct evidence for CO formation was observed."},{"key":"e_1_2_8_66_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-0037-1610329"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.9531020","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.9531020","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.9531020","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,7,7]],"date-time":"2026-07-07T14:25:27Z","timestamp":1783434327000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.9531020"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,5,14]]},"references-count":65,"journal-issue":{"issue":"27","published-print":{"date-parts":[[2026,7,1]]}},"alternative-id":["10.1002\/anie.9531020"],"URL":"https:\/\/doi.org\/10.1002\/anie.9531020","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,5,14]]},"assertion":[{"value":"2026-01-12","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-04-17","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-05-14","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e9531020"}}