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The reversal of polarity, or umpolung, at phosphorus is a conceptually significant transformation leading to new reactivity. While geometrically constrained phosphines have been demonstrated to exhibit electrophilic character, similar behavior for trigonal phosphines is rare. In this study, we report direct experimental evidence of electrophilic behavior in a non\u2010constrained trigonal phosphine enabled by the attachment of a redox\u2010active boron cluster. The diphosphine 1\u2010P\n                    <jats:sup>t<\/jats:sup>\n                    Bu\n                    <jats:sub>2<\/jats:sub>\n                    \u20102\u2010P\n                    <jats:sup>i<\/jats:sup>\n                    Pr\n                    <jats:sub>2<\/jats:sub>\n                    \u2010\n                    <jats:italic>closo<\/jats:italic>\n                    \u2010C\n                    <jats:sub>2<\/jats:sub>\n                    B\n                    <jats:sub>10<\/jats:sub>\n                    H\n                    <jats:sub>10<\/jats:sub>\n                    undergoes selective addition of anionic nucleophiles, including\n                    <jats:sup>n<\/jats:sup>\n                    Bu\n                    <jats:sup>\u2212<\/jats:sup>\n                    and CN\n                    <jats:sup>\u2212<\/jats:sup>\n                    , at its P\n                    <jats:sup>t<\/jats:sup>\n                    Bu\n                    <jats:sub>2<\/jats:sub>\n                    group. These reactions are accompanied by a two\u2010electron reduction of the carborane cage and its conversion from a neutral\n                    <jats:italic>closo<\/jats:italic>\n                    \u2010 to a dianionic\n                    <jats:italic>nido<\/jats:italic>\n                    \u2010 structure, demonstrating that cluster\u2010centered redox activity drives phosphorus\u2010centered electrophilicity. The resulting\n                    <jats:italic>nido<\/jats:italic>\n                    \u2010carboranyl phosphines exhibit enhanced nucleophilicity at the remaining phosphine arm, enabling subsequent trapping with alkyl halides, carbon disulfide, and electron\u2010deficient fluoroarenes. These findings establish redox\u2010active boron clusters as platforms for inducing umpolung and provide a new strategy for accessing ambiphilic reactivity at phosphorus.\n                  <\/jats:p>","DOI":"10.1002\/chem.71090","type":"journal-article","created":{"date-parts":[[2026,5,1]],"date-time":"2026-05-01T15:11:27Z","timestamp":1777648287000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Trigonal Phosphine Umpolung: Electrophilicity Driven by a Redox\u2010Active Boron Cluster"],"prefix":"10.1002","volume":"32","author":[{"given":"Bryce C.","family":"Nussbaum","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biochemistry University of South Carolina  Columbia South Carolina USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mark D.","family":"Smith","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry University of South Carolina  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