Synthesis and reactIVity of a terminal uranium(IV) sulfide supported by siloxide ligands
Andrez J, Pecaut J, Scopelliti R, Kefalidis CE, Maron L, Rosenzweig M, Meyer K, Mazzanti M (2016)
Publication Type: Journal article
Publication year: 2016
Journal
Book Volume: 7
Pages Range: 5846-5856
Journal Issue: 9
DOI: 10.1039/c6sc00675b
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.
Authors with CRIS profile
Michael Rosenzweig
Lehrstuhl für Anorganische und Allgemeine Chemie
Karsten Meyer
Lehrstuhl für Anorganische und Allgemeine Chemie
Involved external institutions
Université Fédérale de Toulouse Midi-Pyrénées
France (FR)
École Polytechnique Fédérale de Lausanne (EPFL)
Switzerland (CH)
University of Grenoble Alpes (UGA) / Université de Grenoble
France (FR)
France (FR)
École Polytechnique Fédérale de Lausanne (EPFL)
Switzerland (CH)
University of Grenoble Alpes (UGA) / Université de Grenoble
France (FR)
How to cite
APA:
Andrez, J., Pecaut, J., Scopelliti, R., Kefalidis, C.E., Maron, L., Rosenzweig, M.,... Mazzanti, M. (2016). Synthesis and reactIVity of a terminal uranium(IV) sulfide supported by siloxide ligands. Chemical Science, 7(9), 5846-5856. https://doi.org/10.1039/c6sc00675b
MLA:
Andrez, Julie, et al. "Synthesis and reactIVity of a terminal uranium(IV) sulfide supported by siloxide ligands." Chemical Science 7.9 (2016): 5846-5856.
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