The Influence of Phosphorus Substituents on the Structures and Solution Speciation of Trivalent Uranium and Lanthanide Phosphinodiboranates
The Influence of Phosphorus Substituents on the Structures and Solution Speciation of Trivalent Uranium and Lanthanide Phosphinodiboranates
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磷取代基对三价铀和镧系膦二硼酸盐结构和溶液形态的影响
DOI：
10.1021/acs.inorgchem.3c02773
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发表时间：
2023
影响因子：
4.6
通讯作者：
Daly, Scott R.
中科院分区：
文献类型：
--
作者：
Zgrabik, Joshua C.;Bhowmick, Rina;Eckstrom, Francesca D.;Harrison, A. Rayford;Fetrow, Taylor V.;Blake, Anastasia V.;Vlaisavljevich, Bess;Daly, Scott R.
在这里，我们报告了磷上带有异丙基和乙基取代基的均配铀和镧系膦二硼酸盐的机械化学合成和表征。通过球磨 UI3(THF)4、SmBr3 或 MI3 与三当量的 K(H3BPiPr2BH3) 制备 M=U、Nd、Sm、Tb 和 Er 的 M(H3BPiPr2BH3)3 配合物。使用K(H3BPEt2BH3)类似地制备M(H3BPEt2BH3)3，其中M=U和Nd，并且通过从Et2O或CH2Cl2中萃取和结晶来纯化络合物。单晶 XRD 研究表明，尽管该系列的金属半径存在显着差异，但所有五种 M(H3BPiPr2BH3)3 均结晶为二聚体。相反，具有较小乙基取代基的Nd(H3BPEt2BH3)3作为配位聚合物结晶。 U(H3BPEt2BH3)3晶体不适合结构分析，但通过溶液法以低产率分离的U(H3BPMe2BH3)3晶体与Nd(H3BPEt2BH3)3是同构的。C6D6中的1H和11B NMR研究表明，所有配合物在溶解时形成单体和低聚物的混合物，并且低聚程度高度依赖于金属半径和磷取代基的大小。对迄今为止报道的所有结构特征铀和镧系膦二硼酸配合物（包括具有较大 Ph 和 tBu 取代基的配合物）的综合分析表明，溶液中的低聚程度可以与单晶 XRD 研究中获得的 B-P-B 角差异相关。密度泛函理论计算，包括结构优化与使用紧密结合方法的构象搜索相结合，复制了一般实验趋势，并揭示了解释不同溶液和固态结构的自由能差异。总的来说，这些结果揭示了从金属配位位点显着移除的磷取代基的空间变化如何对溶液形态、解低聚能量和含有三价 f-金属的均配膦二硼酸配合物的固态结构产生显着影响。
Here, we report the mechanochemical synthesis and characterization of homoleptic uranium and lanthanide phosphinodiboranates with isopropyl and ethyl substituents attached to phosphorus. M(H3BPiPr2BH3)3complexes with M = U, Nd, Sm, Tb, and Er were prepared by ball milling UI3(THF)4, SmBr3, or MI3with three equivalents of K(H3BPiPr2BH3). M(H3BPEt2BH3)3with M = U and Nd were prepared similarly using K(H3BPEt2BH3), and the complexes were purified by extraction and crystallization from Et2O or CH2Cl2. Single-crystal XRD studies revealed that all five M(H3BPiPr2BH3)3crystallize as dimers, despite the significant differences in metal radii across the series. In contrast, Nd(H3BPEt2BH3)3with smaller ethyl substituents crystallized as a coordination polymer. Crystals of U(H3BPEt2BH3)3were not suitable for structural analysis, but crystals of U(H3BPMe2BH3)3isolated in low yield by solution methods were isostructural with Nd(H3BPEt2BH3)3.1H and11B NMR studies in C6D6revealed that all of the complexes form mixtures of monomer and oligomers when dissolved, and the extent of oligomerization was highly dependent on metal radius and phosphorus substituent size. A comprehensive analysis of all structurally characterized uranium and lanthanide phosphinodiboranate complexes reported to date, including those with larger Ph andtBu substituents, revealed that the degree of oligomerization in solution can be correlated to differences in B–P–B angles obtained from single-crystal XRD studies. Density functional theory calculations, which included structural optimizations in combination with conformational searches using tight binding methods, replicated the general experimental trends and revealed free energy differences that account for the different solution and solid-state structures. Collectively, these results reveal how steric changes to phosphorus substituents significantly removed from metal coordination sites can have a significant influence on solution speciation, deoligomerization energies, and the solid-state structure of homoleptic phosphinodiboranate complexes containing trivalent f-metals.
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通讯作者：
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