具有吡唑烷和三唑烷配体的 [Mo12O28(μ-L)8]4-多氧甲基簇的四丁基铵盐

IF 16.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Accounts of Chemical Research Pub Date : 2024-04-30 DOI:10.1134/S0022476624030156

A. V. Konkova, D. V. Evtushok, Y. A. Vorotnikov, I. V. Eltsov, V. V. Yanshole, A. A. Ivanov, M. A. Shestopalov

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引用次数: 0

摘要

摘要在 Bu4NOH 的水溶液中，用四丁基铵在沸腾状态下对 (NH4)4[Mo12O28(μ-L)8]（L = pz（吡唑酸盐）和 trz（1,2,4-三唑酸盐））中的铵阳离子进行了偏析。通过 XRD、1H NMR 和质谱等多种物理化学方法证实了阳离子的取代和阴离子团簇片段的保留。所得到的化合物在有机溶剂中易溶且稳定，因此对其氧化还原特性进行了研究。根据循环伏安数据，L = pz 和 trz 时，化合物表现出 E1/2 = 0.26 V 和 0.61 V 的可逆氧化性。量子化学计算对电子结构进行了研究。结果表明，这些化合物的前沿分子轨道主要由钼 d 轨道组成。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Tetrabutylammonium Salts of [Mo12O28(μ-L)8]4– Polyoxometal Clusters with Pyrazolate and Triazolate Ligands

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Tetrabutylammonium Salts of [Mo12O28(μ-L)8]4– Polyoxometal Clusters with Pyrazolate and Triazolate Ligands

The metathesis of ammonium cations in (NH₄)₄[Mo₁₂O₂₈(μ-L)₈] (L = pz (pyrazolate) and trz (1,2,4-triazolate)) with tetrabutylammonium is performed under boiling in an aqueous solution with Bu₄NOH. The substitution of cations and the preservation of the anionic cluster fragment are confirmed by a number of physicochemical methods such as XRD, ¹H NMR, and mass spectrometry. The resulting compounds are soluble and stable in organic solvents, so their redox properties are studied. According to the cyclic voltammetry data, the compounds exhibit reversible oxidation with E_1/2 = 0.26 V and 0.61 V for L = pz and trz respectively. The electronic structure is studied by quantum chemical calculations. It is shown that the frontier molecular orbitals of these compounds are mainly composed of molybdenum d-orbitals.

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来源期刊

Accounts of Chemical Research 化学-化学综合

CiteScore

31.40

自引率

1.10%

发文量

312

审稿时长

2 months

期刊介绍： Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.