Jump to main content
Jump to site search

Issue 9, 2016
Previous Article Next Article

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

Author affiliations

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 13 Feb 2016, accepted on 09 May 2016 and first published on 10 May 2016


Article type: Edge Article
DOI: 10.1039/C6SC00677A
Citation: Chem. Sci., 2016,7, 5857-5866
  • Open access: Creative Commons BY license
  •   Request permissions

    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

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements