Uranium(IV) Terminal Hydrosulfido and Sulfido Complexes: The Nature of the Uranium–Sulfur Bond

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-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.


Published in:
Chem. Sci.
Year:
2016
Publisher:
Cambridge, Royal Soc Chemistry
ISSN:
2041-6539
Laboratories:




 Record created 2016-05-10, last modified 2018-09-13


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