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Metathesis of a UV imido complex: a route to a terminal UV sulfide.
Journal article

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

  • Kelly RP Institut des Sciences et Ingénierie Chimiques , Ecole Polytechnique Fédérale de Lausanne (EPFL) , 1015 Lausanne , Switzerland . Email: marinella.mazzanti@epfl.ch.
  • Falcone M Institut des Sciences et Ingénierie Chimiques , Ecole Polytechnique Fédérale de Lausanne (EPFL) , 1015 Lausanne , Switzerland . Email: marinella.mazzanti@epfl.ch.
  • Lamsfus CA Université de Toulouse et CNRS INSA , UPS , CNRS , UMR 5215 , LPCNO , 135 avenue de Rangueil , 31077 Toulouse , France.
  • Scopelliti R Institut des Sciences et Ingénierie Chimiques , Ecole Polytechnique Fédérale de Lausanne (EPFL) , 1015 Lausanne , Switzerland . Email: marinella.mazzanti@epfl.ch.
  • Maron L Université de Toulouse et CNRS INSA , UPS , CNRS , UMR 5215 , LPCNO , 135 avenue de Rangueil , 31077 Toulouse , France.
  • 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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  • 2017-10-04
Published in:
  • Chemical science. - 2017
General Chemistry
English 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 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CNAd. 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, SCNAd. 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.
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  • English
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gold
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https://sonar.ch/global/documents/97114
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