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Issue 6, 2015
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CS2 activation at uranium(III) siloxide ate complexes: the effect of a Lewis acidic site

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Abstract

Multimetallic cooperative binding of heteroallenes provides an attractive route to their activation, but the reduction of CS2 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 CS2 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(OtBu)3)4], 1, leads preferentially to the reductive disproportionation of CS2 to K2CS3 and CS. The crystal structure of the thiocarbonate intermediate complex [U(OSi(OtBu)3)43−κ222−CS3)K2(18c6)2], 3, isolated from the toluene reaction mixture has been determined. In contrast, the heterobimetallic complex [U(OSi(OtBu)3)4K], 2, promotes preferentially the reductive dimerization of CS2 to K2C2S4 and K2C3S5. The [K2C2S4(DMSO)3]n, 5, and [U(OSi(OtBu)3)4K2(C3S5)]n, 6, polymeric compounds were isolated from this reaction and structurally characterized.

Graphical abstract: CS2 activation at uranium(iii) siloxide ate complexes: the effect of a Lewis acidic site

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Publication details

The article was received on 26 Aug 2014, accepted on 10 Nov 2014 and first published on 10 Nov 2014


Article type: Paper
DOI: 10.1039/C4DT02585G
Citation: Dalton Trans., 2015,44, 2650-2656
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    CS2 activation at uranium(III) siloxide ate complexes: the effect of a Lewis acidic site

    C. Camp, O. Cooper, J. Andrez, J. Pécaut and M. Mazzanti, Dalton Trans., 2015, 44, 2650
    DOI: 10.1039/C4DT02585G

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