Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
Laboratory for Quantum Magnetism, Institute of Physics, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
J Am Chem Soc. 2020 Mar 25;142(12):5538-5542. doi: 10.1021/jacs.0c01204. Epub 2020 Mar 11.
Out of the 14 lanthanide (Ln) ions, molecular complexes of Ln(IV) were known only for cerium and more recently terbium. Here we demonstrate that the +IV oxidation state is also accessible for the large praseodymium (Pr) cation. The oxidation of the tetrakis(triphenysiloxide) Pr(III) ate complex, [KPr(OSiPh)(THF)], , with [N(CHBr)][SbCl], affords the Pr(IV) complex [Pr(OSiPh)(MeCN)], , which is stable once isolated. The solid state structure, UV-visible spectroscopy, magnetometry, and cyclic voltammetry data along with the DFT computations of the complex unambiguously confirm the presence of Pr(IV).
在 14 种镧系元素（Ln）中，人们仅知道镧（IV）和最近的铽（IV）的分子配合物。在这里，我们证明+IV 氧化态也适用于大的镨（Pr）阳离子。用[N(CHBr)][SbCl]氧化四（三苯硅基）Pr(III) 烷配合物[KPr(OSiPh)(THF)]，得到 Pr(IV) 配合物[Pr(OSiPh)(MeCN)]，一旦分离出来就很稳定。配合物的固态结构、紫外可见光谱、磁学、循环伏安法数据以及 DFT 计算都明确证实了 Pr(IV)的存在。
