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Synthesis and reactivity of a terminal uranium(iv) sulfide supported by siloxide ligands.
Journal article

Synthesis and reactivity of a terminal uranium(iv) sulfide supported by siloxide ligands.

  • Andrez J Institut des Sciences et Ingénierie Chimiques Ecole Polytechnique Fédérale de Lausanne (EPFL) , 1015 Lausanne , Switzerland . Email: marinella.mazzanti@epfl.ch.
  • Pécaut J Univ. Grenoble Alpes , INAC-SyMMES , RICC , F-38000 Grenoble , France.
  • Scopelliti R Institut des Sciences et Ingénierie Chimiques Ecole Polytechnique Fédérale de Lausanne (EPFL) , 1015 Lausanne , Switzerland . Email: marinella.mazzanti@epfl.ch.
  • Kefalidis CE Université de Toulouse et CNRS INSA , UPS , CNRS , UMR 5215 , LPCNO , 135 avenue de Rangueil , 31077 Toulouse , France.
  • Maron L Université de Toulouse et CNRS INSA , UPS , CNRS , UMR 5215 , LPCNO , 135 avenue de Rangueil , 31077 Toulouse , France.
  • Rosenzweig MW Department of Chemistry and Pharmacy , Inorganic Chemistry , Friedrich-Alexander University Erlangen-Nürnberg , Egerlandstraße 1 , 91058 Erlangen , Germany.
  • Meyer K Department of Chemistry and Pharmacy , Inorganic Chemistry , Friedrich-Alexander University Erlangen-Nürnberg , Egerlandstraße 1 , 91058 Erlangen , Germany.
  • Mazzanti M Institut des Sciences et Ingénierie Chimiques Ecole Polytechnique Fédérale de Lausanne (EPFL) , 1015 Lausanne , Switzerland . Email: marinella.mazzanti@epfl.ch.
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  • 2018-07-24
Published in:
  • Chemical science. - 2016
English The reactions of the tetrasiloxide U(iii) complexes [U(OSi(O t Bu)3)4K] and [U(OSi(O t Bu)3)4][K18c6] with 0.5 equiv. of triphenylphosphine sulfide led to reductive S-transfer reactions, affording the U(iv) sulfide complexes [SU(OSi(O t Bu)3)4K2]2, 1, and [{SU(OSi(O t Bu)3)4K2}2(μ-18c6)], 2, with concomitant formation of the U(iv) complex [U(OSi(O t Bu)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(O t Bu)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(O t Bu)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(O t Bu)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.
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  • English
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https://folia.unifr.ch/global/documents/99717
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