Crystalline Diuranium-Phosphinidiide and -μ-Phosphido Complexes with Symmetric and Asymmetric UPU Cores

Thomas Rookes, Benedict Gardner, Gabor Balazs, Matthew Gregson, Floriana Tuna, Ashley Wooles, Manfred Scheer, Stephen Liddle

    Research output: Contribution to journalArticlepeer-review


    Reaction of [U(TrenTIPS)(PH2)] (1, TrenTIPS = N(CH2CH2NSiPri 3)3) with C6H5CH2K and [U(TrenTIPS)(THF)][BPh4] (2) afforded a rare diuranium-parent-phosphinidiide complex [{U(TrenTIPS)}2(μ-PH)] (3). Treatment of 3 with C6H5CH2K and two equivalents of benzo-15-crown-5 ether (B15C5) gave the diuranium-μ- phosphido complex [{U(TrenTIPS)}2(μ-P)][K(B15C5)2] (4). Alternatively, reaction of [U(TrenTIPS)(PH)][Na(12C4)2] (5, 12C4 = 12-crown-4 ether) with [U{N(CH2CH2NSiMe2But)2CH2CH2NSi(Me)(CH2)(But)}] (6) produced the diuranium-μ-phosphido complex [{U(TrenTIPS)}(μ- P){U(TrenDMBS)}][Na(12C4)2] [7, TrenDMBS = N(CH2CH2NSiMe2But)3]. Compounds 4 and 7 are unprecedented examples of uranium-phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium-phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles.
    Original languageEnglish
    Pages (from-to)10495-10500
    Number of pages6
    JournalAngewandte Chemie - International Edition
    Issue number35
    Early online date24 Jul 2017
    Publication statusPublished - 21 Aug 2017


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