Issue 9, 2016

Uranium(iv) terminal hydrosulfido and sulfido complexes: insights into the nature of the uranium–sulfur bond

Abstract

Herein, we report the synthesis and characterization of a series of terminal uranium(IV) hydrosulfido and sulfido complexes, supported by the hexadentate, tacn-based ligand framework (Ad,MeArO)3tacn3− (= trianion of 1,4,7-tris(3-(1-adamantyl)-5-methyl-2-hydroxybenzyl)-1,4,7-triazacyclononane). The hydrosulfido complex [((Ad,MeArO)3tacn)U–SH] (2) is obtained from the reaction of H2S with the uranium(III) starting material [((Ad,MeArO)3tacn)U] (1) in THF. Subsequent deprotonation with potassium bis(trimethylsilyl)amide yields the mononuclear uranium(IV) sulfido species in good yields. With the aid of dibenzo-18-crown-6 and 2.2.2-cryptand, it was possible to isolate a terminal sulfido species, capped by the potassium counter ion, and a “free” terminal sulfido species with a well separated cation/anion pair. Spectroscopic and computational analyses provided insights into the nature of the uranium–sulfur bond in these complexes.

Graphical abstract: Uranium(iv) terminal hydrosulfido and sulfido complexes: insights into the nature of the uranium–sulfur bond

Supplementary files

Article information

Article type
Edge Article
Submitted
13 Kol 2016
Accepted
09 Mot 2016
First published
10 Mot 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2016,7, 5857-5866

Uranium(IV) terminal hydrosulfido and sulfido complexes: insights into the nature of the uranium–sulfur bond

M. W. Rosenzweig, A. Scheurer, C. A. Lamsfus, F. W. Heinemann, L. Maron, J. Andrez, M. Mazzanti and K. Meyer, Chem. Sci., 2016, 7, 5857 DOI: 10.1039/C6SC00677A

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