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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,Me ArO) 3 tacn 3À (¼ trianion of 1,4,7-tris(3-(1-adamantyl)-5-methyl-2-hydroxybenzyl)-1,4,7-triazacyclononane). The hydrosulfido complex [((Ad,Me ArO) 3 tacn)U-SH] (2) is obtained from the reaction of H 2 S with the uranium(III) starting material [((Ad,Me ArO) 3 tacn)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.
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Michael Rosenzweig, Andreas Scheurer, Carlos Lamsfus, Frank Heinemann, Laurent Maron, et al.. Uranium( iv ) terminal hydrosulfido and sulfido complexes: insights into the nature of the uranium–sulfur bond. Chemical Science , The Royal Society of Chemistry, 2016, 7 (9), pp.5857-5866. ⟨10.1039/c6sc00677a⟩. ⟨hal-01968915⟩

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