Issue 8, 2017

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

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

Supplementary files

Article information

Article type
Edge Article
Submitted
10 mar 2017
Accepted
25 may 2017
First published
05 iyn 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 5319-5328

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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