Accessing the plus IV Oxidation State in Molecular Complexes of Praseodymium
Accessing the plus IV Oxidation State in Molecular Complexes of Praseodymium
复制标题
DOI：
10.1021/jacs.0c01204
复制
发表时间：
2020-03-25
影响因子：
15
通讯作者：
Mazzanti, Marinella
中科院分区：
文献类型：
--
作者：
Willauer, Aurelien R.;Palumbo, Chad T.;Mazzanti, Marinella
在14种镧系（Ln）离子中，已知Ln（IV）的分子配合物仅为铈和最近的铽。在这里，我们证明了+IV氧化态也可用于大的镨（Pr）阳离子。四（三苯基硅氧化物）Pr（III）盐配合物[KPr(OSiPh3)(4)(THF)(3)]， 1-Pr-Ph与[N(C6H4Br)(3)][SbCl6]氧化得到Pr（IV）配合物[Pr(OSiPh3)(4)(MeCN)(2)], 2-Pr- ph，该配合物分离后稳定。固体结构、紫外可见光谱、磁强学和循环伏安法数据以及2-Pr-Ph配合物的DFT计算明确证实了Pr（IV）的存在。
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(OSiPh3)(4)(THF)(3)], 1-Pr-Ph, with [N(C6H4Br)(3)][SbCl6], affords the Pr(IV) complex [Pr(OSiPh3)(4)(MeCN)(2)], 2-Pr-Ph, which is stable once isolated. The solid state structure, UV-visible spectroscopy, magnetometry, and cyclic voltammetry data along with the DFT computations of the 2-Pr-Ph complex unambiguously confirm the presence of Pr(IV).