SYNTHESIS AND REACTIONS OF URANIUM(IV) TETRATHIOLATE COMPLEXES

Uranium(IV) tetrathiolate complexes were made by (a) reaction of U(NEt(2))(4) with RSH (R = Et, Pr-i, Bu(n) or Bu(t)), (b) treatment of U(BH4)(4) with RSH (R = Bu(n) or Ph) or of U(SBu(n))(4) with PhSH or (c) oxidation of uranium metal by RSSR (R = Et, Pr-i 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(t)SH and Me(2)C=CH2. Reaction of U(SPri)(4) with [NEt(3)H][BPh(4)] in the presence of hexamethylphosphoric triamide (hmpa) afforded the cationic compound [U(SPri)(2)(hmpa)(4)][BPh(4)](2) which presents a trans-octahedral crystal structure. Iodinolysis of U(SPri)(4) in pyridine led to the formation of [U(SPri)(2)I-2(py)(3)] which adopts a pentagonal-bipyramidal configuration in its crystalline form. The trithiocarbonate ((PrS)-S-i)(2)C=S was obtained by reaction of U(SPri)(4) with CS2.