Lanthanide Tetrabromoterephthalates: Promotion of Cycloaddition Reactions of Carbon Dioxide without Preactivation, Solvent, and Co-Catalyst at Ambient Pressure through Structural Design

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-09-18 DOI:10.1021/acs.inorgchem.5c02558

Malee Sinchow, , , Thammanoon Chuasaard, , , Natthiti Chiangraeng, , , Stephanie A. Bird, , , Piyarat Nimmanpipug, , , Nobuto Yoshinari, , and , Apinpus Rujiwatra*,

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引用次数: 0

Abstract

To catalyze the cycloaddition reactions of carbon dioxide and epoxides without additional solvent or cocatalyst under ambient pressure, [Ln^III₂(tbta)₂(COO)₂(DMF)₄] (Ln^III = Sm^III (I^Sm), Eu^III (I^Eu), and Gd^III (I^Gd); H₂tbta = tetrabromoterephthalic acid; DMF = dimethylformamide) were synthesized and characterized. Their crystal structures were elucidated. Ln^III were selected because of their hard acidity and tendency to function without preactivation. H₂tbta was chosen because of its abundant bromide substituents and its potential acidic and basic sites. [Eu^III₂(tbta)₂(COO)₂(H₂O)₆]·5H₂O (II^Eu) and [Gd^III(tbta)_1.5(DMF)(H₂O)₄]·H₂O (III^Gd) were additionally prepared through the transformation of I^Eu and I^Gd. The catalytic activities of I^Sm, I^Eu, and I^Gd were explored using a range of epoxides under ambient pressure without additional solvent and cocatalyst. They showed selective activities toward epichlorohydrin. The best performances, in terms of turnover number and turnover frequency, were obtained at 90 °C and 12 h (I^Sm: 307 and 26 h^–1; I^Eu: 327 and 27 h^–1; I^Gd: 340 and 28 h^–1). Unfortunately, they were unstable after catalysis due to the loss of bromide, which is their essential limitation. However, they demonstrated the possibility of using an organic linker to activate the epoxide and the potential for solid cocatalysts. Computational studies of structural transformation and the feasibility of substituting DMF with ECH were also conducted.

To catalyze the cycloaddition reactions of carbon dioxide and epoxides without additional solvent and cocatalyst under ambient pressure, [Ln^III₂(tbta)₂(COO)₂(DMF)₄] (Ln^III = Sm^III (I^Sm), Eu^III (I^Eu) and Gd^III (I^Gd); H₂tbta = tetrabromoterephthalic acid; DMF = dimethylformamide) were synthesized and characterized. Computational studies of structural transformation and the feasibility of the substitution of DMF by ECH were conducted.

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镧系四溴对苯二甲酸盐：通过结构设计促进二氧化碳在环境压力下无预活化、溶剂和助催化剂的环加成反应。

为了在常压下催化二氧化碳和环氧化物的环加成反应，无需额外的溶剂或助催化剂，[LnIII2(tbta)2(COO)2(DMF)4] (LnIII = SmIII (ISm), EuIII （IEu）和GdIII (IGd)；H2tbta =四溴对苯二甲酸；合成了二甲基甲酰胺（DMF）并对其进行了表征。阐明了它们的晶体结构。选择LnIII是因为它们的硬酸性和不需要预活化的功能倾向。选择H2tbta是因为它具有丰富的溴取代基和潜在的酸性和碱性位点。通过IEu和IGd的转化，制备了[EuIII2(tbta)2(COO)2(H2O)6]·5H2O （IIEu）和[GdIII(tbta)1.5(DMF)(H2O)4]·H2O （IIIGd）。在不添加溶剂和助催化剂的情况下，用一系列环氧化物考察了ISm、IEu和IGd在常压下的催化活性。它们对环氧氯丙烷具有选择性。在90°C和12 h下（ISm: 307和26 h-1； IEu: 327和27 h-1； IGd: 340和28 h-1），周转次数和周转频率最佳。不幸的是，由于溴化物的损失，它们在催化后不稳定，这是它们的本质限制。然而，他们证明了使用有机连接剂激活环氧化物的可能性以及固体助催化剂的潜力。并对结构转换和用ECH取代DMF的可行性进行了计算研究。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.