Reductive silylation of uranyl mediated by iminosemiquinone ligands
Reductive silylation of uranyl mediated by iminosemiquinone ligands
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亚氨基半醌配体介导的铀酰还原硅烷化
DOI：
10.1016/j.poly.2019.06.028
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发表时间：
2019
期刊：
影响因子：
2.6
通讯作者：
Suzanne C. Bart
中科院分区：
文献类型：
--
作者：
Ezra J. Coughlin;Suzanne C. Bart
报道了铀酰类化合物（dippisq）_2UO_2 THF的化学计量硅烷基化反应，该反应具有两个还原的亚氨基半醌配体。这些配体自由基促进铀6+还原为4+，这伴随着铀酰部分与两当量Me 3SiBr的甲硅烷基化和氧化配体的释放。中间体（Me 3SiO）2UBr 2（OPPh 3）2在U-O键裂解之前通过进一步加入Me 3SiBr分离，产生UBr 4（OPPh 3）2。U-O键断裂也可以在一锅反应中进行，通过用Me 2SiCl 2处理（dippisq）2UO 2 THF，形成UCl 4（OPPh 3）2和聚合的甲硅烷基产物（O双键SiMe 2）n，伴随着氧化配体的损失。在每种情况下，同位素18 O标记实验突出了铀酰氧原子掺入到反应中释放的所得硅氧烷中。
Stoichiometric silylation of the uranyl species, (dippisq)2UO2THF, which features two reduced iminosemiquinone ligands, is reported. These ligand radicals facilitate the reduction of uranium 6+ to 4+, which is accompanied by silylation of the uranyl moiety with two equivalents of Me3SiBr and release of the oxidized ligand. The intermediate, (Me3SiO)2UBr2(OPPh3)2, is isolated prior to U–O bond cleavage by further addition of Me3SiBr, producing UBr4(OPPh3)2. U–O bond scission can also be performed in a one-pot reaction, by treating (dippisq)2UO2THF with Me2SiCl2, forming UCl4(OPPh3)2and polymeric silyl products, (Odouble bondSiMe2)n, with concomitant loss of oxidized ligand. In each case, isotopic18O labeling experiments highlight the incorporation of the uranyl oxygen atoms into the resulting siloxanes released in the reactions.
影响因子：
4.6
作者：
Arnold, Polly L.;Pecharman, Anne-Frederique;Love, Jason B.
通讯作者：
Love, Jason B.
影响因子：
21.8
作者：
Arnold, Polly L.;Pecharman, Anne-Frederique;Love, Jason B.
通讯作者：
Love, Jason B.