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The reaction product adopts a Pacman conformation with two P\u2212Cl moieties, one in <jats:italic>exo<\/jats:italic> and one in <jats:italic>endo<\/jats:italic> position. It represents the first non\u2010metal compound of calix[4]pyrrole Schiff base ligands and of Pacman ligands in general. The spatial neighborhood of the two phosphorus atoms enables cooperative reactions. As a first example, the chloride abstraction with AgOTf is presented, yielding a macrocyclic dication with two embedded phosphorus(III) monocations, which both undergo a cooperative, internal activation reaction with an adjacent C=N double bond. This intramolecular redox process affords two pentacoordinated phosphorus(V) centers within the Pacman dication. All reaction products were fully characterized and all results are supported by computations.<\/jats:p>","DOI":"10.1002\/chem.202103983","type":"journal-article","created":{"date-parts":[[2021,11,10]],"date-time":"2021-11-10T22:06:07Z","timestamp":1636581967000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["A Phosphorus\u2010Based Pacman Dication Generated by Cooperative Self\u2010Activation of a Pacman Phosphane"],"prefix":"10.1002","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1368-5507","authenticated-orcid":false,"given":"Liesa","family":"Eickhoff","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Chemie Universit\u00e4t Rostock  Albert-Einstein-Str. 3a 18059 Rostock Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0254-2033","authenticated-orcid":false,"given":"Leon","family":"Ohms","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Universit\u00e4t Rostock  Albert-Einstein-Str. 3a 18059 Rostock Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9450-3407","authenticated-orcid":false,"given":"Jonas","family":"Bresien","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Universit\u00e4t Rostock  Albert-Einstein-Str. 3a 18059 Rostock Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0868-9987","authenticated-orcid":false,"given":"Alexander","family":"Villinger","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Universit\u00e4t Rostock  Albert-Einstein-Str. 3a 18059 Rostock Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0285-2595","authenticated-orcid":false,"given":"Dirk","family":"Michalik","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Universit\u00e4t Rostock  Albert-Einstein-Str. 3a 18059 Rostock Germany"},{"name":"Leibniz-Institut f\u00fcr Katalyse e. 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