Chelating Borohydrides for Lanthanides and Actinides: Structures, Mechanochemistry, and Case Studies with Phosphinodiboranates
Chelating Borohydrides for Lanthanides and Actinides: Structures, Mechanochemistry, and Case Studies with Phosphinodiboranates
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DOI：
10.1021/acs.inorgchem.9b01628
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发表时间：
2020-01-06
影响因子：
4.6
通讯作者：
Daly, Scott R.
中科院分区：
文献类型：
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作者：
Fetrow, Taylor V.;Bhowinick, Rina;Daly, Scott R.
在这篇论坛文章中，我们回顾了螯合硼氢化物配体称为氨基二硼酸酯（H3BNR2BH 3-）和膦基二硼酸酯（H3BPR2BH 3-）的三价f-元素配合物的合成的发展。介绍了机械化学法制备分子硼氢化物配合物的优点和发展历史，沿着了机械化学法合成M-2（（H3BPBu 2BH 3）-Bu-t）（6）的新结果，其中M = U，Nd，Tb，Er，Lu（1 - 5）。报告了1 - 5的多核NMR、IR和单晶X-射线衍射数据，以及互补密度泛函理论计算，以揭示它们在有和没有四氢呋喃的情况下的结构和反应性的差异。结果表明，如何机械化学可以用来访问f-元素络合物与螯合硼的改进和可重复的产量，这是一个重要的一步，对研究性质的镧系元素和锕系元素膦二硼配合物与不同的磷取代基。这些结果的相关性是由已知的影响f-元素硼化物的挥发性和应用程序，需要开发的挥发性f-元素络合物的结构因素的讨论。
In this Forum Article, we review the development of chelating borohydride ligands called aminodiboranates (H3BNR2BH3-) and phosphinodiboranates (H3BPR2BH3-) for the synthesis of trivalent f-element complexes. The advantages and history of using mechanochemistry to prepare molecular borohydride complexes are described along with new results demonstrating the mechanochemical synthesis of M-2 ((H3BPBu2BH3)-Bu-t)(6), where M = U, Nd, Tb, Er, and Lu (1-5). Multinuclear NMR, IR, and single-crystal X-ray diffraction data are reported for 1-5 alongside complementary density functional theory calculations to reveal differences in their structure and reactivity with and without tetrahydrofuran. The results demonstrate how mechanochemistry can be used to access f-element complexes with chelating borohydrides in improved and reproducible yields, which is an important step toward investigating the properties of lanthanide and actinide phosphinodiboranate complexes with different phosphorus substituents. The relevance of these results is contextualized by a discussion of structural factors known to influence the volatility of f-element borohydrides and applications that require the development of volatile f-element complexes.