均三甲苯锚定的三（芳氧基）配体的镧系配合物中的金属与配体还原反应
Metal versus Ligand Reduction in Ln Complexes of a Mesitylene-Anchored Tris(Aryloxide) Ligand.
作者信息
Palumbo Chad T, Halter Dominik P, Voora Vamsee K, Chen Guo P, Chan Alan K, Fieser Megan E, Ziller Joseph W, Hieringer Wolfgang, Furche Filipp, Meyer Karsten, Evans William J
机构信息
Department of Chemistry , University of California , Irvine , California 92697-2025 , United States.
Department of Chemistry and Pharmacy, Inorganic Chemistry , Friedrich-Alexander-University Erlangen-Nürnberg (FAU) , Egerlandstrasse 1 , D-91058 Erlangen , Germany.
出版信息
Inorg Chem. 2018 Mar 5;57(5):2823-2833. doi: 10.1021/acs.inorgchem.7b03236. Epub 2018 Feb 19.
The synthesis of 4f Ln complexes of the tris(aryloxide) mesitylene ligand, ((ArO)mes), with Ln = La, Ce, Pr, Sm, and Yb, and their reduction with potassium have revealed that this ligand system can be redox active with some metals. Protonolysis of [Ln(N(SiMe))] (Ln = La, Ce, Pr, Sm, Yb) with the tris(phenol) (ArOH)mes yielded the Ln complexes [((ArO)mes)Ln] (Ln = La, Ce, Pr, Sm, Yb), 1-Ln. Single electron reduction of each 4f complex, 1-Ln, using potassium yielded the reduced products, [K(2.2.2-cryptand)][((ArO)mes)Ln] (Ln = La, Ce, Pr, Sm, Yb), 2-Ln. The Sm and Yb complexes have properties consistent with the presence of Ln ions with traditional 4f electron configurations. However, the La, Ce, and Pr complexes appear to formally contain Ln ions and ((ArO)mes) ligands. Structural comparisons of the [((ArO)mes)Ln] and [((OAr)mes)Ln] complexes along with UV-vis absorption and EPR spectroscopy as well as density functional theory calculations support these ground state assignments.
三（芳氧基）均三甲苯配体（（ArO）mes）与镧系元素（Ln = La、Ce、Pr、Sm和Yb）形成的4f镧系配合物的合成，以及它们用钾进行的还原反应表明，该配体体系对某些金属具有氧化还原活性。用三酚（ArOH）mes对[Ln（N（SiMe））]（Ln = La、Ce、Pr、Sm、Yb）进行质子解反应，得到镧系配合物[（（ArO）mes）Ln]（Ln = La、Ce、Pr、Sm、Yb），即1-Ln。使用钾对每个4f配合物1-Ln进行单电子还原，得到还原产物[K（2.2.2-穴醚）][（（ArO）mes）Ln]（Ln = La、Ce、Pr、Sm、Yb），即2-Ln。Sm和Yb配合物的性质与具有传统4f电子构型的Ln离子的存在一致。然而，La、Ce和Pr配合物似乎正式包含Ln离子和（（ArO）mes）配体。[（（ArO）mes）Ln]和[（（OAr）mes）Ln]配合物的结构比较以及紫外可见吸收光谱、电子顺磁共振光谱和密度泛函理论计算支持这些基态归属。
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