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Issue 2, 2014
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Two-electron versus one-electron reduction of chalcogens by uranium(III): synthesis of a terminal U(V) persulfide complex

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Abstract

The reaction of the tripodal tris-amido U(III) complex [U{(SiMe2NPh)3–tacn}] (tacn = 1,4,7-triazacyclononane), 1, with 0.0625 and 0.25 equiv. of elemental sulfur affords the sulfide-bridged U(IV) complex [{U((SiMe2NPh)3–tacn)}2(μ-S)], 2, and the terminal persulfide U(V) complex [U{(SiMe2NPh)3–tacn}(η2-S2)], 4, respectively, in good yield. Two different electronic structures, U(V) persulfide and U(IV) supersulfide, were computed for complex 4 at the DFT level. The results show that complex 4 is best described as a U(V) persulfide species with a significant sulfur contribution. X-ray, magnetism and electrochemistry data support this description. Complex 4 is the first example of a terminal U(V) persulfide and of a two-electron reduction of S8 by a U(III) complex. Complex 4 behaves as a S-atom transfer agent when reacted with PPh3, affording the persulfide-bridged diuranium(IV) complex [{U((SiMe2NPh)3–tacn)}2(μ-η22-S2)], 5, and S[double bond, length as m-dash]PPh3.

Graphical abstract: Two-electron versus one-electron reduction of chalcogens by uranium(iii): synthesis of a terminal U(v) persulfide complex

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Publication details

The article was received on 01 Oct 2013, accepted on 29 Oct 2013 and first published on 29 Oct 2013


Article type: Edge Article
DOI: 10.1039/C3SC52742E
Citation: Chem. Sci., 2014,5, 841-846
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    Two-electron versus one-electron reduction of chalcogens by uranium(III): synthesis of a terminal U(V) persulfide complex

    C. Camp, M. A. Antunes, G. García, I. Ciofini, I. C. Santos, J. Pécaut, M. Almeida, J. Marçalo and M. Mazzanti, Chem. Sci., 2014, 5, 841
    DOI: 10.1039/C3SC52742E

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