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Issue 8, 2017
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Metathesis of a UV imido complex: a route to a terminal UV sulfide

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Abstract

Herein, we report the synthesis and characterisation of the first terminal uranium(V) sulfide and a related UV trithiocarbonate complex supported by sterically demanding tris(tert-butoxy)siloxide ligands. The reaction of the potassium-bound UV imido complex, [U(NAd){OSi(OtBu)3}4K] (4), with CS2 led to the isolation of perthiodicarbonate [K(18c6)]2[C2S6] (6), with concomitant formation of the UIV complex, [U{OSi(OtBu)3}4], and S[double bond, length as m-dash]C[double bond, length as m-dash]NAd. In contrast, the reaction of the UV imido complex, [K(2.2.2-cryptand)][U(NAd){OSi(OtBu)3}4] (5), with one or two equivalents of CS2 afforded the trithiocarbonate complex, [K(2.2.2-cryptand)][U(CS3){OSi(OtBu)3}4] (7), which was isolated in 57% yield, with concomitant elimination of the admantyl thiocyanate product, S[double bond, length as m-dash]C[double bond, length as m-dash]NAd. Complex 7 is likely formed by fast nucleophilic addition of a UV terminal sulfide intermediate, resulting from the slow metathesis reaction of the imido complex with CS2, to a second CS2 molecule. The addition of a solution of H2S in thf (1.3 eq.) to 4 afforded the first isolable UV terminal sulfide complex, [K(2.2.2-cryptand)][US{OSi(OtBu)3}4] (8), in 41% yield. Based on DFT calculations, triple-bond character with a strong covalent interaction is suggested for the U–S bond in complex 7.

Graphical abstract: Metathesis of a UV imido complex: a route to a terminal UV sulfide

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Publication details

The article was received on 10 Mar 2017, accepted on 25 May 2017 and first published on 05 Jun 2017


Article type: Edge Article
DOI: 10.1039/C7SC01111C
Citation: Chem. Sci., 2017,8, 5319-5328
  • Open access: Creative Commons BY license
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    Metathesis of a UV imido complex: a route to a terminal UV sulfide

    R. P. Kelly, M. Falcone, C. A. Lamsfus, R. Scopelliti, L. Maron, K. Meyer and M. Mazzanti, Chem. Sci., 2017, 8, 5319
    DOI: 10.1039/C7SC01111C

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