H. C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, IN, 47907, USA.
Department of Chemistry, Youngstown State University, Youngstown, OH, 44555, USA.
Angew Chem Int Ed Engl. 2017 Jan 19;56(4):1097-1100. doi: 10.1002/anie.201609838. Epub 2016 Dec 19.
General reductive silylation of the UO 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 X (L) (X=Cl, Br, I, OTf; L=triphenylphosphine oxide, 2,2'-bipyridyl) followed by two equivalents of a silyl (pseudo)halide, R Si-X (R=aryl, alkyl, H; X=Cl, Br, I, OTf, SPh), cleanly affords (R SiO) UX (L) in high yields. Support is included for the key step in the process, reduction of U to U . 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 or two equivalents of Me SiCl results in direct conversion of the uranyl to uranium(IV) tetrachloride. Full spectroscopic and structural characterization of the siloxide products is reported.
UO 阳离子很容易在室温下进行一锅两步计量反应，发生普遍的还原硅烷化反应，形成铀(IV)硅氧烷。向 UO X (L)（X=Cl、Br、I、OTf；L=三苯基氧化膦，2,2'-联吡啶）中添加两当量的烷基化试剂，然后再添加两当量的硅（假）卤化物 R Si-X（R=芳基、烷基、H；X=Cl、Br、I、OTf、SPh），可高收率地得到（R SiO）UX（L）。该过程的关键步骤（将 U 还原为 U ）得到了支持。该方法适用于广泛的市售铀酰盐、硅卤化物和烷基化试剂。在此方案下，一当量的 SiCl 或两当量的 Me SiCl 可将铀酰直接转化为四氯化铀。报道了硅氧烷产物的全光谱和结构特征。
