In search of tris(trimethylsilylcyclopentadienyl) thorium
In search of tris(trimethylsilylcyclopentadienyl) thorium
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寻找三(三甲基甲硅烷基环戊二烯基)钍
DOI：
10.1039/c9dt03674a
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发表时间：
2019
影响因子：
4
通讯作者：
Evans, William J.
中科院分区：
文献类型：
--
作者：
Wedal, Justin C.;Bekoe, Samuel;Ziller, Joseph W.;Furche, Filipp;Evans, William J.
用钾石墨还原Cp′ 3 ThCl、Cp′ 3 ThBr和Cp′ 3 ThI（Cp′ = C5 H4 SiMe 3）生成深蓝色溶液，其反应性和光谱性质与Cp′ 3 Th的形成一致。溶液的EPR和UV-可见光谱与晶体学表征的三（三）Th（III）配合物：[C5 H3（SiMe 3）2] 3 Th，（C5 Me 4 H）3 Th，（C5 tBu 2 H3）3 Th和（C5 Me 5）3 Th的EPR和UV-可见光谱相似。密度泛函理论（DFT）分析表明，紫外-可见光谱与Cp′ 3 Th一致，而不是[Cp′ 3 ThBr]1−。虽然Cp′ 3 Th的单晶尚未分离，但蓝色溶液与Me 3SiCl、I2和HCCPh反应，分别得到Cp′ 3 Th预期的产物，即Cp′ 3 ThCl、Cp′ 3 ThI和Cp′ 3 Th（CCPh）。与MeI反应得到Cp′ 3 ThI和Cp′ 3 ThMe的混合物。尚未观察到蓝色溶液进一步还原为Cp′-连接的Th（II）络合物的证据。Cp′ 3 Th Me和（Cp′ 3 Th）2（μ-O）的晶体结构也被确定为这些研究的一部分。
Reduction of Cp′3ThCl, Cp′3ThBr, and Cp′3ThI (Cp′ = C5H4SiMe3) with potassium graphite generates dark blue solutions with reactivity and spectroscopic properties consistent with the formation of Cp′3Th. The EPR and UV-visible spectra of the solutions are similar to those of crystallographically-characterized tris(cyclopentadienyl) Th(III) complexes: [C5H3(SiMe3)2]3Th, (C5Me4H)3Th, (C5tBu2H3)3Th, and (C5Me5)3Th. Density functional theory (DFT) analysis indicates that the UV-visible spectrum is consistent with Cp′3Th and not [Cp′3ThBr]1−. Although single crystals of Cp′3Th have not been isolated, the blue solution reacts with Me3SiCl, I2, and HCCPh to afford products expected from Cp′3Th, namely, Cp′3ThCl, Cp′3ThI, and Cp′3Th(CCPh), respectively. Reactions with MeI give mixtures of Cp′3ThI and Cp′3ThMe. Evidence for further reduction of the blue solutions to a Cp′-ligated Th(II) complex has not been observed. The crystal structures of Cp′3ThMe and (Cp′3Th)2(μ-O) were also determined as part of these studies.