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Facile Reductive Silylation of UO 2 2+ to Uranium(IV) Chloride
Author(s) -
Kiernicki John J.,
Zeller Matthias,
Bart Suzanne C.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201609838
Subject(s) - chemistry , silylation , uranyl , halide , uranium , reagent , stoichiometry , alkyl , aryl , chloride , triphenylphosphine , inorganic chemistry , medicinal chemistry , organic chemistry , catalysis , ion , materials science , metallurgy
General reductive silylation of the UO 2 2+ cation occurs readily in a one‐pot, two‐step stoichiometric reaction at room temperature to form uranium(IV) siloxides. Addition of two equivalents of an alkylating reagent to UO 2 X 2 (L) 2 (X=Cl, Br, I, OTf; L=triphenylphosphine oxide, 2,2′‐bipyridyl) followed by two equivalents of a silyl (pseudo)halide, R 3 Si‐X (R=aryl, alkyl, H; X=Cl, Br, I, OTf, SPh), cleanly affords (R 3 SiO) 2 UX 2 (L) 2 in high yields. Support is included for the key step in the process, reduction of U VI to U V . This procedure is applicable to a wide range of commercially available uranyl salts, silyl halides, and alkylating reagents. Under this protocol, one equivalent of SiCl 4 or two equivalents of Me 2 SiCl 2 results in direct conversion of the uranyl to uranium(IV) tetrachloride. Full spectroscopic and structural characterization of the siloxide products is reported.