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

Kelly RP, Falcone M, Lamsfus CA, Scopelliti R, Maron L, Meyer K, Mazzanti M (2017)

Publication Type: Journal article

Publication year: 2017

Journal

Chemical Science Royal Society of Chemistry

Book Volume: 8

Pages Range: 5319-5328

Journal Issue: 8

DOI: 10.1039/c7sc01111c

Abstract

Herein, we report the synthesis and characterisation of the first terminal uranium(v) sulfide and a related U^V trithiocarbonate complex supported by sterically demanding tris(tert-butoxy)siloxide ligands. The reaction of the potassium-bound U^V 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 U^IV complex, [U{OSi(OtBu)3}4], and SCNAd. In contrast, the reaction of the U^V 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, SCNAd. Complex 7 is likely formed by fast nucleophilic addition of a U^V 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 U^V 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.

Authors with CRIS profile

Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

École Polytechnique Fédérale de Lausanne (EPFL)

Switzerland (CH) Université Fédérale de Toulouse Midi-Pyrénées

France (FR)

How to cite

APA:

Kelly, R.P., Falcone, M., Lamsfus, C.A., Scopelliti, R., Maron, L., Meyer, K., & Mazzanti, M. (2017). Metathesis of a UV imido complex: A route to a terminal UV sulfide. Chemical Science, 8(8), 5319-5328. https://doi.org/10.1039/c7sc01111c

MLA:

Kelly, Rory P., et al. "Metathesis of a UV imido complex: A route to a terminal UV sulfide." Chemical Science 8.8 (2017): 5319-5328.

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