Venturing Past Uranium: Synthesis of a Np(IV) Polyoxomolybdate–Alkoxide Sandwich Complex

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2024-11-20 DOI:10.1021/acs.inorgchem.4c04428

Leyla R. Valerio, Dominic Shiels, Lauren M. Lopez, Andrew W. Mitchell, Matthias Zeller, Suzanne C. Bart, Ellen M. Matson

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Abstract

The synthesis of a Np(IV) polyoxomolybdate–alkoxide sandwich complex, (TBA)₂[Np{Mo₅O₁₃(OMe)₄NO}₂] (TBA = tetrabutylammonium), is reported. This compound represents a rare example of a neptunium polyoxometalate cluster isolated outside of water, allowing for characterization of its electrochemical properties in nonaqueous solvents. Complexation of An(IV) cations fine-tunes the redox properties of the cluster, with the observed four reversible reductive events varying slightly both in potential and peak separation depending on the actinide present. The new Np(IV) complex also shows an irreversible event assigned to oxidation of Np(IV) to Np(V). New methodology for facile ¹⁷O enrichment of (TBA)₂[Mo₅O₁₃(OMe)₄NO][Na(MeOH)] is presented, which provides a simple pathway to ¹⁷O enriched analogues of the sandwich complexes discussed (Zr(IV), Hf(IV), Th(IV), U(IV), U(V), Np(IV)). ¹⁷O NMR spectroscopy subsequently provides insights into both the nature of metal–oxygen bonding, as well as the influence of unpaired f-electrons on the local environment of the oxygen nuclei.

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超越铀：镎（IV）多氧钼酸盐-氧化铝夹心络合物的合成

报告了一种 Np（IV）多氧钼酸盐-氧化铝夹心复合物 (TBA)2[Np{Mo5O13(OMe)4NO}2] （TBA = 四丁基铵）的合成过程。该化合物是分离于水之外的多氧金属镎簇的一个罕见实例，可用于表征其在非水溶剂中的电化学特性。与 An（IV）阳离子的络合微调了该簇的氧化还原特性，观察到的四种可逆还原事件在电位和峰值分离方面略有不同，这取决于存在的锕系元素。新的 Np（IV）复合物还显示出 Np（IV）氧化成 Np（V）的不可逆事件。本文介绍了对 (TBA)2[Mo5O13(OMe)4NO][Na(MeOH)]进行 17O 富集的新方法，为获得所讨论的夹心配合物（Zr(IV)、Hf(IV)、Th(IV)、U(IV)、U(V)、Np(IV)）的 17O 富集类似物提供了一条简单的途径。17O NMR 光谱随后提供了有关金属-氧键性质以及未配对 f 电子对氧原子核局部环境影响的见解。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.