Triscyclopentadienyl uranium thiolates and selenolates

Add time:07/30/2019    Source:sciencedirect.com

Triscyclopentadienyl uranium (IV) thiolates were prepared by two principal methods namely (1) substitution of the chloride group of [U(cp)3(Cl)] (cp = η-C5H5) by Sr− and (2) oxidation of the trivalent precursors [U(cp)3(THF)] (THF = tetrahydrofuran), [U(C5H4SiMe3)3] and [U(C5H4tBu)3] with the disulfide RSSR (R = Me, Et, iPr, tBu or Ph).Similar treatment with MeSeSeMe afforded [U(cp)3(SeMe)] and [U(C5H4SiMe3)3(SeMe)]. The crystal structure of [U(cp)3(SMe)] was determined. Several reactions ofthese complexes are described, namely cleavage of the U-S bond by acidic substrates or iodine, insertion of Cs2 and CO2 into the U-S bond, and reduction into the corresponding U(III) anions. The synthesis, structure and reactivity of the thiolate compounds are compared with those of the alkoxide analogues.

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