NDLI: $CS_{2}$ activation at uranium(III) siloxide ate complexes: the effect of a Lewis acidic site

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Andrez, Julie Camp, Clément Mazzanti, Marinella Cooper, Oliver Pécaut, Jacques
Description	Author Affiliation: Camp C ( Univ. Grenoble Alpes, INAC-SCIB, RICC, F-38000 Grenoble, France.)
Abstract	Multimetallic cooperative binding of heteroallenes provides an attractive route to their activation, but the reduction of $CS_{2}$ at heterobimetallic sites, associating an electron-rich metal with a main group Lewis acid has not been explored. Here we show that the presence of a heterometallic U, K site plays an important role in the $CS_{2}$ reduction by uranium(III) complexes of the electron-rich and the sterically demanding tris(tert-butoxy)siloxide ligand. Specifically, the ion-pair complex $[K(18c6)][U(OSi(O^{t}Bu)_{3})_{4}],$ 1, leads preferentially to the reductive disproportionation of $CS_{2}$ to $K_{2}CS_{3}$ and CS. The crystal structure of the thiocarbonate intermediate complex $[U(OSi(O^{t}Bu)_{3})_{4}$ $(μ_{3−}κ^{2}:κ^{2}:κ^{2−}CS_{3})K_{2}(18c6)_{2}],$ 3, isolated from the toluene reaction mixture has been determined. In contrast, the heterobimetallic complex $[U(OSi(O^{t}Bu)_{3})_{4}K],$ 2, promotes preferentially the reductive dimerization of $CS_{2}$ to $K_{2}C_{2}S_{4}$ and $K_{2}C_{3}S_{5}.$ The $[K_{2}C_{2}S_{4}(DMSO)_{3}]_{n},$ 5, and $[U(OSi(O^{t}Bu)_{3})_{4}K_{2}(C_{3}S_{5})]_{n},$ 6, polymeric compounds were isolated from this reaction and structurally characterized.
ISSN	14779226
Issue Number	6
Journal	Dalton Trans.
Volume Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-02-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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