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However, catalytic turnover has remained largely restricted to hydrodefluorination pathways reliant on metallomimetic reductive elimination. Herein, we report a defluorinative functionalization platform mediated by zwitterionic pnictinidenes that enables the formation of diverse C\u2013X bonds (X = C, O, S, N, P, Se) from polyfluoro(hetero)arenes under mild conditions. Combined experimental and DFT studies reveal that, although a Sb(I)\/Sb(III) redox cycle could be accessed, catalysis instead proceeds through Sb(III)\u2013F species that promote C\u2013F substitution via a redox\u2010neutral manifold. These findings establish catalyst speciation as a decisive mechanistic branch point, showing how strategies to modulate ligand scrambling events may enable alternative pnictogen\u2010based redox or redox\u2010neutral manifolds.<\/jats:p>","DOI":"10.1002\/anie.6579940","type":"journal-article","created":{"date-parts":[[2026,7,21]],"date-time":"2026-07-21T19:11:15Z","timestamp":1784661075000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Speciation\u2010Controlled C\u2013F Bond Functionalization Enabled by Zwitterionic Pnictinidenes"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7471-1831","authenticated-orcid":false,"given":"Irene","family":"S\u00e1nchez\u2010Sordo","sequence":"first","affiliation":[{"name":"Department of Chemistry Imperial College London Molecular Sciences Research Hub  London 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