Ernst Moritz J, Petrov Andrey, Schröder Mirjam, Corzilius Björn, Müller Christian
Institute of Chemistry and Biochemistry, Freie Universität Berlin, Fabeckstr. 34/36, 14195, Berlin, Germany.
Leibniz-Institute for Catalysis, Albert-Einstein-Str. 29a, 18059, Rostock, Germany.
Angew Chem Int Ed Engl. 2025 Jun 10;64(24):e202505853. doi: 10.1002/anie.202505853. Epub 2025 Apr 27.
The addition of [2.2.2]cryptand to alkali metal heptaphosphides MP (M = Na, K) leads to the formation of [M([2.2.2]cryptand)][cyclo-P] salts. Although the cyclo-P anion is spectroscopically known since the 1980s, it was so far prepared and handled only in solution. By complexing the alkali metal cation with [2.2.2]cryptand, the product was found to be surprisingly stable in the solid state. Cyclo-P , which is isolobal to the well-known cyclopentadienide anion, was now characterized crystallographically for the first time in its uncoordinated form and in the presence of the weakly coordinating cations [M(2.2.2-cryptand)] (M = Na, K). The structural elucidation proves its planar D symmetry, not only as ligand in different sandwich complexes but also in its uncoordinated form. Cyclo-P was further characterized by UV/Visis spectroscopy in solution and in the solid state by Raman and P MAS NMR spectroscopy. The reaction of [Na([2.2.2]cryptand)][cyclo-P] with LiCp* and FeCl yields the ferrocene derivative [Cp*Fe(cyclo-P)].
在碱金属七磷化物MP（M = Na、K）中加入[2.2.2]穴醚会生成[M([2.2.2]穴醚)][环 - P]盐。尽管环 - P阴离子自20世纪80年代起就为光谱学所熟知，但迄今为止它仅在溶液中制备和处理。通过将碱金属阳离子与[2.2.2]穴醚络合，发现该产物在固态下出奇地稳定。与著名的环戊二烯基阴离子等瓣的环 - P，首次以其未配位形式并在弱配位阳离子[M(2.2.2 - 穴醚)]（M = Na、K）存在的情况下通过晶体学进行了表征。结构解析证明了它具有平面D对称性，不仅在不同夹心配合物中作为配体，而且在其未配位形式中也是如此。环 - P还通过溶液中的紫外/可见光谱以及固态下的拉曼光谱和磷的魔角旋转核磁共振光谱进行了进一步表征。[Na([2.2.2]穴醚)][环 - P]与LiCp和FeCl反应生成二茂铁衍生物[CpFe(环 - P)]。
