Franz Roman, Bartek Máté, Bruhn Clemens, Kelemen Zsolt, Pietschnig Rudolf
Institute for Chemistry, CINSaT, University of Kassel Heinrich-Plett-Straße 40 34132 Kassel Germany
Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics Műegyetem Rkp 3 1111 Budapest Hungary
Chem Sci. 2024 Nov 25;16(1):139-146. doi: 10.1039/d4sc06823h. eCollection 2024 Dec 18.
Triphospha[3]ferrocenophane Fe(CH-PTip)PCl (Tip = 2,4,6-tri(isopropyl)phenyl) has been prepared and its suitability to generate the corresponding bisphosphanylphosphenium ion has been explored. By formal addition of P to the latter, an unprecedented tetraphosphenium ion forms which likewise is capable of P transfer and qualifies as Lewis superacid based on its computed fluoride ion affinity. As a solid, this species is stable and conveniently storable, featuring a remarkably long P-P bond (2.335(5) Å). From this tetraphosphenium ion, known and unprecedented triphosphenium ions have been generated P transfer in solution, including a triphosphenium ion with P-H functionalities. Moreover, the latter has been obtained by tautomeric rearrangement from the corresponding hydrophosphane precursor. The bonding situation and details of the P transfer have been investigated by DFT calculations and experimental methods like multinuclear NMR spectroscopy and SC-XRD.
已制备出三磷[3]二茂铁膦烷Fe(CH-PTip)PCl（Tip = 2,4,6-三（异丙基）苯基），并探索了其生成相应双膦基磷鎓离子的适用性。通过向后一种物质正式添加磷，形成了一种前所未有的四磷鎓离子，该离子同样能够进行磷转移，并且根据其计算出的氟离子亲和力可被视为路易斯超强酸。作为一种固体，该物质稳定且便于储存，具有非常长的P-P键（2.335(5) Å）。通过溶液中的磷转移，从这种四磷鎓离子生成了已知的和前所未有的三磷鎓离子，包括具有P-H官能团的三磷鎓离子。此外，后者是通过相应的氢膦前体的互变异构重排获得的。通过DFT计算以及多核NMR光谱和SC-XRD等实验方法研究了键合情况和磷转移的细节。
