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Issue 9, 2016
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Synthesis and reactivity of a terminal uranium(IV) sulfide supported by siloxide ligands

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Abstract

The reactions of the tetrasiloxide U(III) complexes [U(OSi(OtBu)3)4K] and [U(OSi(OtBu)3)4][K18c6] with 0.5 equiv. of triphenylphosphine sulfide led to reductive S-transfer reactions, affording the U(IV) sulfide complexes [SU(OSi(OtBu)3)4K2]2, 1, and [{SU(OSi(OtBu)3)4K2}2(μ-18c6)], 2, with concomitant formation of the U(IV) complex [U(OSi(OtBu)3)4]. Addition of 1 equiv. of 2.2.2-cryptand to complex 1 resulted in the isolation of a terminal sulfide complex, [SU(OSi(OtBu)3)4K][Kcryptand], 3. The crucial role of the K+ Lewis acid in these reductive sulfur transfer reactions was confirmed, since the formation of complex 3 from the reaction of the U(III) complex [U(OSi(OtBu)3)4][Kcryptand] and 0.5 equiv. of PPh3S was not possible. Reactivity studies of the U(IV) sulfide complexes showed that the sulfide is easily transferred to CO2 and CS2 to afford S-functionalized products. Moreover, we have found that the sulfide provides a convenient precursor for the synthesis of the corresponding U(IV) hydrosulfide, {[(SH)U(OSi(OtBu)3)4][K18c6]}, 5, after protonation with PyHCl. Finally, DFT calculations were performed to investigate the nature of the U–S bond in complexes 1, 3 and 5. Based on various analyses, triple-bond character was suggested for the U–S bond in complexes 1 and 3, while double-bond character was determined for the U–SH bond in complex 5.

Graphical abstract: Synthesis and reactivity of a terminal uranium(iv) sulfide supported by siloxide ligands

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Publication details

The article was received on 13 Feb 2016, accepted on 08 Apr 2016 and first published on 10 May 2016


Article type: Edge Article
DOI: 10.1039/C6SC00675B
Citation: Chem. Sci., 2016,7, 5846-5856
  • Open access: Creative Commons BY license
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    Synthesis and reactivity of a terminal uranium(IV) sulfide supported by siloxide ligands

    J. Andrez, J. Pécaut, R. Scopelliti, C. E. Kefalidis, L. Maron, M. W. Rosenzweig, K. Meyer and M. Mazzanti, Chem. Sci., 2016, 7, 5846
    DOI: 10.1039/C6SC00675B

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