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Issue 3, 2014
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Reactivity of uranium(iv) bridged chalcogenido complexes UIV–E–UIV (E = S, Se) with elemental sulfur and selenium: synthesis of polychalcogenido-bridged uranium complexes

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Abstract

We report the syntheses, electronic properties, and molecular structures of a series of polychalcogenido-bridged dinuclear uranium species. These complexes are supported by the sterically encumbering but highly flexible, single N-anchored tris(aryloxide) chelator (AdArO)3N3−. Reaction of an appropriate uranium precursor, either the U(III) starting material, [((AdArO)3N)U(DME)], or the dinuclear mono-chalcogenido-bridged uranium(IV/IV) compounds [{((AdArO)3N)U(DME)}2(μ-E)] (E = S, Se), with elemental sulfur or selenium, yields new complexes with a variety of bridging chalcogenide entities μ-Emn (E = S, m = 2, n = 1 or 2 and E = Se, m = 2, 4; n = 2). Activation of the heavy chalcogens typically requires either a coordinatively unsaturated, strongly-reducing metal complex or a compound with a metal–metal bond. Since uranium complexes in the +IV oxidation state, are generally considered rather unreactive, the observed reaction of the here employed uranium(IV)/(IV) species with elemental chalcogens is fairly remarkable.

Graphical abstract: Reactivity of uranium(iv) bridged chalcogenido complexes UIV–E–UIV (E = S, Se) with elemental sulfur and selenium: synthesis of polychalcogenido-bridged uranium complexes

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Article information


Submitted
08 Oct 2013
Accepted
07 Nov 2013
First published
08 Nov 2013

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2014,5, 942-950
Article type
Edge Article

Reactivity of uranium(IV) bridged chalcogenido complexes UIV–E–UIV (E = S, Se) with elemental sulfur and selenium: synthesis of polychalcogenido-bridged uranium complexes

S. M. Franke, F. W. Heinemann and K. Meyer, Chem. Sci., 2014, 5, 942
DOI: 10.1039/C3SC52799A

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