title: Facile Reductive Silylation of UO22+to Uranium(IV) Chloride.
abstract: General reductive silylation of the UO22+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 UO2X2(L)2(X=Cl, Br, I, OTf; L=triphenylphosphine oxide, 2,2'-bipyridyl) followed by two equivalents of a silyl (pseudo)halide, R3Si-X (R=aryl, alkyl, H; X=Cl, Br, I, OTf, SPh), cleanly affords (R3SiO)2UX2(L)2in high yields. Support is included for the key step in the process, reduction of UVIto UV. This procedure is applicable to a wide range of commercially available uranyl salts, silyl halides, and alkylating reagents. Under this protocol, one equivalent of SiCl4or two equivalents of Me2SiCl2results in direct conversion of the uranyl to uranium(IV) tetrachloride. Full spectroscopic and structural characterization of the siloxide products is reported.
authors.affiliation: H. C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, IN, 47907, USA.
authors.forename: John J
authors.initials: JJ
authors.lastname: Kiernicki
authors.affiliation: H. C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, IN, 47907, USA.|Department of Chemistry, Youngstown State University, Youngstown, OH, 44555, USA.
authors.forename: Matthias
authors.initials: M
authors.lastname: Zeller
authors.affiliation: H. C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, IN, 47907, USA.
authors.forename: Suzanne C
authors.initials: SC
authors.lastname: Bart
keywords: alkylation; oxo complexes; reduction; reductive silylation; uranium