The rational design and synthesis of the Trapen ligand (1, tris(2-aminobenzyl)amine) with a tripodal scaffold is reported. Treatment of Trapen with n-BuLi and TMSCl results in the formation of the corresponding complex [(Trapen^TMS)(Li)₃] (2). In particular, 2 reacts with UCl₄ to give the important synthon uranium(IV) complex [U(Trapen^TMS)(Cl)] (3) with all of the nitrogen atoms bound to the uranium(IV) center. Moreover, the pseudohalogen congener [U(Trapen^TMS)(OCP)] (4) or the azide analogue [U(Trapen^TMS)(N₃)] (5) could be obtained when [U(Trapen^TMS)(Cl)] (3) was treated with NaOCP(dioxane)_2.5 or NaN₃ by a salt metathesis approach. In addition, the reaction of KC₈ with [U(Trapen^TMS)(Cl)] (3) did not afford the desired U(III) complex but produced the unexpected bridging diuranium oxo complex [U(Trapen^TMS)₂(μ-O)] (6). All of the compounds were isolated in the solid state and characterized by NMR, X-ray crystal diffraction, and FT-IR, and UV–vis–NIR as well as elemental analyses and SQUID magnetization measurements. The combined experimental analyses and chemical calculations support all of the formal uranium(IV) species.

中文翻译：

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用于U（IV）的三脚架配体的合理设计：U–Cl物种的合成与表征及其反应性的见解

报道了具有三脚架支架的Trapen配体（1，三（2-氨基苄基）胺）的合理设计和合成。用n -BuLi和TMSC1处理Trapen导致形成相应的复合物[（Trapen ^TMS）（Li）₃ ]（2）。特别是2与UCl ₄反应，生成重要的合成子铀（IV）络合物[U（Trapen ^TMS）（Cl）]（3），所有氮原子均键合在铀（IV）中心。此外，拟卤素同源物[U（Trapen ^TMS）（OCP）]（4）或叠氮化物类似物[U（Trapen ^TMS）（N ₃）]（5）可以通过盐复分解法用NaOCP（二恶烷）_2.5或NaN ₃处理[U（Trapen ^TMS）（Cl）]（3）来获得。此外，KC ₈与[U（Trapen ^TMS）（Cl）]（3）的反应未得到所需的U（III）配合物，但产生了意外的桥接二氧铀配合物[U（Trapen ^TMS）₂ [ O）]（6）。所有化合物均以固态分离，并通过NMR，X射线晶体衍射，FT-IR，UV-vis-NIR以及元素分析和SQUID磁化强度测量进行表征。实验分析和化学计算相结合，支持所有形式的铀（IV）物种。