Eickhoff Liesa, Ohms Leon, Bresien Jonas, Villinger Alexander, Michalik Dirk, Schulz Axel
Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059, Rostock, Germany.
Leibniz-Institut für Katalyse e. V., Albert-Einstein-Str. 29a, 18059, Rostock, Germany.
Chemistry. 2022 Jan 13;28(3):e202103983. doi: 10.1002/chem.202103983. Epub 2021 Nov 24.
Formal coordination of phosphorus(III) by a calix[4]pyrrole Schiff base ligand was achieved through the reaction of this ligand with PCl 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.
通过杯[4]吡咯席夫碱配体与PCl在碱性条件下的反应，实现了磷(III)与该配体的形式配位。反应产物采用“吃豆人”构象，带有两个P-Cl部分，一个处于外型，一个处于内型。它代表了杯[4]吡咯席夫碱配体以及一般“吃豆人”配体的首个非金属化合物。两个磷原子的空间邻位使得协同反应成为可能。作为第一个例子，展示了用AgOTf进行的氯原子抽取反应，生成了一种大环双阳离子，其中包含两个嵌入的磷(III)单阳离子，这两个单阳离子都与相邻的C=N双键发生协同的内部活化反应。这种分子内氧化还原过程在“吃豆人”双阳离子内产生了两个五配位的磷(V)中心。所有反应产物都得到了充分表征，所有结果都得到了计算的支持。
