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A Phosphorus‐Based Pacman Dication Generated by Cooperative Self‐Activation of a Pacman Phosphane
Author(s) -
Eickhoff Liesa,
Ohms Leon,
Bresien Jonas,
Villinger Alexander,
Michalik Dirk,
Schulz Axel
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202103983
Subject(s) - dication , chemistry , intramolecular force , ligand (biochemistry) , pyrrole , phosphorus , chloride , base (topology) , medicinal chemistry , photochemistry , stereochemistry , molecule , organic chemistry , mathematical analysis , biochemistry , receptor , mathematics
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.