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A series of P\n                    <jats:sup>III<\/jats:sup>\n                    \u2212X (X=Cl, Br, I) dicationic triflate salts supported by benzyl\u2010 and allyl\u2010substituted 2,6\u2010bis(benzimidazole\u20102\u2010yl)pyridine (BZIMPY) ligands is synthesized. Surprisingly, treatment of these with R\n                    <jats:sub>3<\/jats:sub>\n                    PO (R=Et, Oct) results in reduction to BZIMPY\u2010ligated P\n                    <jats:sup>I<\/jats:sup>\n                    monocationic triflate salts while treatment with Ph\n                    <jats:sub>3<\/jats:sub>\n                    P reduces but also substitutes the compound to produce Ph\n                    <jats:sub>3<\/jats:sub>\n                    P\u2010BZIMPY\u2010ligated P\n                    <jats:sup>I<\/jats:sup>\n                    dicationic triflate salts. The mechanisms of these surprising reductions are probed experimentally and rationalized computationally. The P\n                    <jats:sup>III<\/jats:sup>\n                    \u2212X dications are shown to be strong Lewis acids both experimentally and computationally and to readily behave as X\n                    <jats:sup>+<\/jats:sup>\n                    , PX, and P\n                    <jats:sup>+<\/jats:sup>\n                    transfer agents in reactions with phosphines, NHCs, and diazabutadienes. The P\n                    <jats:sup>I<\/jats:sup>\n                    mono\u2010 and dications are shown to be very effective P\n                    <jats:sup>+<\/jats:sup>\n                    transfer agents when treated similarly. Oxidation from a monocationic P\n                    <jats:sup>I<\/jats:sup>\n                    salt back to the dicationic P\n                    <jats:sup>III<\/jats:sup>\n                    \u2212X (X=Cl, Br) salt was achieved by treatment with N\u2010chlorosuccinimide (NCS) or N\u2010bromosuccinimide (NBS). Full characterization is reported using multinuclear nuclear magnetic resonance spectroscopy, elemental analysis, and single\u2010crystal X\u2010ray diffractometry where suitable crystals were isolated.\n                  <\/jats:p>","DOI":"10.1002\/chem.202302558","type":"journal-article","created":{"date-parts":[[2023,9,7]],"date-time":"2023-09-07T22:24:02Z","timestamp":1694125442000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["P\n                    <sup>I<\/sup>\n                    and P\n                    <sup>III<\/sup>\n                    Ions Supported by BZIMPY Ligands"],"prefix":"10.1002","volume":"29","author":[{"given":"James H. 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