Crown ether supported alkali metal phosphides : synthesis, structures and bonding

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Krämer, Felix and Crabbe, Michelle H. and Kennedy, Alan R. and Weetman, Catherine E. and Fernández, Israel and Mulvey, Robert E. (2025) Crown ether supported alkali metal phosphides : synthesis, structures and bonding. Chemistry - A European Journal, 31 (51). e02127. ISSN 1521-3765 (https://doi.org/10.1002/chem.202502127)

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Abstract

Herein we present the synthesis and full characterization of the previously unpresented lithium diphenyl phosphides Li(15-crown-5)PPh2 (1Li) and Li(12-crown-4)PPh2 (2Li) as well as the heavy homologues Rb(18-crown-6)PPh2 (1Rb) and Cs(18-crown-6)PPh2 (1Cs). We thus complete the series of crown ether coordinated alkali metal diphenyl phosphides and reveal that the structural diversity increases upon descending the group. Including the previously reported Na and K derivatives, we performed a detailed study of the title compounds in solution that strongly indicated all of them are monomers with an alkali metal phosphide AM–P interaction. We further investigated the influence of the phosphorus-bound substituents on the bond between the Cs(18-crown-6) and the phosphide fragment. For this purpose, we synthesized and characterized two new cesium phosphides, alkyl-aryl Cs(18-crown-6)PtBuPh (4Cs) and bis-alkyl Cs(18-crown-6)PtBu2 (5Cs). We observed here that the heavy alkali metals Rb and Cs favor coordination via π-arene interactions over the P donor dative interactions. Finally, we used state-of-the-art quantum chemical methods to analyze the bonding situation in the title series of compounds.

ORCID iDs

Krämer, Felix, Crabbe, Michelle H., Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Weetman, Catherine E. ORCID logoORCID: https://orcid.org/0000-0001-5643-9256, Fernández, Israel and Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
  • Item type:Article
    ID code:93567
    Dates:
    Date
    Event
    11 September 2025
    Published
    3 August 2025
    Published Online
    23 July 2025
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:24 Jul 2025 11:00
    Last modified:15 Oct 2026 00:18
    URI:https://strathprints.strath.ac.uk/id/eprint/93567
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