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Article Dans Une Revue Chemical Science Année : 2014

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

Résumé

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-η2:η2-S2)], 5, and S[double bond, length as m-dash]PPh3.

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Chimie
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Dates et versions

hal-01877477 , version 1 (19-09-2018)

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Clément Camp, Maria Augusta Antunes, Gregorio García, Ilaria Ciofini, Isabel C Santos, et al.. Two-electron versus one-electron reduction of chalcogens by uranium (III): synthesis of a terminal U (V) persulfide complex. Chemical Science, 2014, 5 (2), pp.841--846. ⟨10.1039/C3SC52742E⟩. ⟨hal-01877477⟩
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