Department of Chemistry , The University of Iowa , E331 Chemistry Building , Iowa City , Iowa 52242 , United States.
Department of Chemistry , The University of South Dakota , 414 East Clark Street , Vermillion , South Dakota 57069 , United States.
Inorg Chem. 2020 Jan 6;59(1):48-61. doi: 10.1021/acs.inorgchem.9b01628. Epub 2019 Aug 30.
In this Forum Article, we review the development of chelating borohydride ligands called aminodiboranates (HBNRBH) and phosphinodiboranates (HBPRBH) 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(HBPBuBH), where M = U, Nd, Tb, Er, and Lu (-). Multinuclear NMR, IR, and single-crystal X-ray diffraction data are reported for - 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.
在这篇论坛文章中，我们回顾了用于合成三价 f 族元素配合物的螯合硼氢化物配体，即氨基二硼酸盐（HBNRBH）和膦二硼酸盐（HBPRBH）的发展。描述了使用机械化学制备分子硼氢化物配合物的优点和历史，以及新的结果表明，M（HBPBuBH）的机械化学合成，其中 M = U、Nd、Tb、Er 和 Lu（-）。报道了 - 的多核 NMR、IR 和单晶 X 射线衍射数据，以及补充的密度泛函理论计算，以揭示它们在有无四氢呋喃存在时的结构和反应性的差异。结果表明，机械化学如何可用于以提高和可重复的产率获得具有螯合硼氢化物的 f 族元素配合物，这是研究具有不同磷取代基的镧系和锕系膦二硼酸盐配合物性质的重要步骤。通过讨论已知影响 f 族元素硼氢化物挥发性的结构因素以及需要开发挥发性 f 族元素配合物的应用，使这些结果具有相关性。
