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More specifically, the generation of phosphanyl radicals [PR\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sup>\u2022<\/jats:sup>\n                    under mild conditions and selective subsequent transformations of these species have recently been the focus of research efforts. Bi\u2500P bond homolysis offers intriguing opportunities for creating [PR\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sup>\u2022<\/jats:sup>\n                    radical species under mild conditions. Here we report the bismuth\u2010mediated transformation of aryl\u2010 and alkyl\u2010substituted phosphanes to the corresponding diphosphanes. Steric and electronic parameters that allow for rapid phosphanyl radical generation have been investigated. Subsequently, the thermally induced phosphanyl radical generation from diphosphanes is tested, revealing a persistent phosphanyl radical. Mechanistic pathways for the stereochemical inversion of phosphorus centers are discussed. Analytical techniques include (VT\u2010)NMR spectroscopy, single\u2010crystal x\u2010ray diffraction, EPR spectroscopy, and density functional theory (DFT) calculations.\n                  <\/jats:p>","DOI":"10.1002\/chem.71573","type":"journal-article","created":{"date-parts":[[2026,8,25]],"date-time":"2026-08-25T11:55:34Z","timestamp":1787658934000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Phosphanyl Radicals From Bismuth\u2010Mediated Reactions and Sterically Encumbered Diphosphanes"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2747-0809","authenticated-orcid":false,"given":"Sascha","family":"Reith","sequence":"first","affiliation":[{"name":"Department of Chemistry Philipps\u2010University Marburg  Marburg Germany"},{"name":"Marburg Center for Quantum Materials and Sustainable Technologies  Marburg 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