P+ addition and transfer involving a tetraphosphenium ion

Franz, Roman and Bartek, Máté and Bruhn, Clemens and Kelemen, Zsolt and Pietschnig, Rudolf (2024) P+ addition and transfer involving a tetraphosphenium ion. CHEMICAL SCIENCE, 16. pp. 139-146. ISSN 2041-6520

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Abstract

Triphospha[3]ferrocenophane Fe(C5H4-PTip)2PCl (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 via 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

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