Synthesis and reactions of uranium(IV) tetrathiolate complexes

Abstract

Uranium(IV) tetrathiolate complexes were made by (a) reaction of U(NEt₂)₄ with RSH (R = Et, Prⁱ, Buⁿ or Bu^t), (b) treatment of U(BH₄)₄ with RSH (R = Buⁿ or Ph) or of U(SBuⁿ)₄ with PhSH or (c) oxidation of uranium metal by RSSR (R = Et, Prⁱ or Ph). Rearrangement of [U(SBu^t)₄(py)₃](py = pyridine) in toluene gave the trinuclear cluster [U₃S(SBu^t)₁₀] with liberation of Bu^tSH and Me₂CCH₂. Reaction of U(SPrⁱ)₄ with [NEt₃H][BPh₄] in the presence of hexamethylphosphoric triamide (hmpa) afforded the cationic compound [U(SPrⁱ)₂(hmpa)₄][BPh₄]₂ which presents a trans-octahedral crystal structure. Iodinolysis of U(SPrⁱ)₄ in pyridine led to the formation of [U(SPrⁱ)₂l₂(py)₃] which adopts a pentagonal-bipyramidal configuration in its crystalline form. The trithiocarbonate (PrⁱS)₂CS was obtained by reaction of U(SPrⁱ)₄ with CS₂.