A Phosphorus‐Based Pacman Dication Generated by Cooperative Self‐Activation of a Pacman Phosphane

Formal coordination of phosphorus(III) by a calix[4]pyrrole Schiff base ligand was achieved through the reaction of this ligand with PCl(3) under basic conditions. The reaction product adopts a Pacman conformation with two P−Cl moieties, one in exo and one in endo position. It represents the first non‐metal 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.