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一种基于镓的路易斯超强酸的罕见实例:Ga(OTeF)₅的合成与反应活性

A Rare Example of a Gallium-Based Lewis Superacid: Synthesis and Reactivity of Ga(OTeF).

作者信息

Fischer Lukas, Hoffmann Kurt F, Riedel Sebastian

机构信息

Fachbereich Biologie, Chemie, Pharmazie, Institut für Chemie und Biochemie - Anorganische Chemie, Freie Universität Berlin, Fabeckstraße 34/36, Berlin, 14195, Germany.

出版信息

Chemistry. 2024 Nov 21;30(65):e202403266. doi: 10.1002/chem.202403266. Epub 2024 Nov 3.

Abstract

The Lewis superacid Ga(OTeF) has been synthesized and characterized, revealing a monomeric structure in solution and a dimeric structure in the solid state. Isolated adducts of Ga(OTeF) with strong and weak Lewis bases have been characterized spectroscopically as well as by single-crystal X-ray diffractometry. The Lewis acidity of this new species has been evaluated by means of different experimental and theoretical methods, which has allowed to classify it as one of only a few examples of a gallium-based Lewis superacid. The high Lewis acidity of Ga(OTeF) was used to amplify the strength of the Brønsted acid HOTeF, leading to the protonation of diethyl ether. Furthermore, Ga(OTeF) was utilized to access the strong oxidizing system Ga(OTeF)/Xe(OTeF) in SOClF, which was successfully employed in the synthesis of the dimethyl chloronium salt [Cl(CH)][Ga(OTeF)], a strong electrophilic methylation reagent.

摘要

路易斯超酸Ga(OTeF)已被合成并表征,结果表明其在溶液中为单体结构,在固态中为二聚体结构。通过光谱学以及单晶X射线衍射法对分离出的Ga(OTeF)与强、弱路易斯碱的加合物进行了表征。已通过不同的实验和理论方法评估了这种新物质的路易斯酸度,这使其被归类为少数几种基于镓的路易斯超酸之一。Ga(OTeF)的高路易斯酸度被用于增强布朗斯特酸HOTeF的强度,从而导致二乙醚质子化。此外,Ga(OTeF)被用于在SOClF中制备强氧化体系Ga(OTeF)/Xe(OTeF),该体系成功用于合成二甲基氯鎓盐[Cl(CH)][Ga(OTeF)],一种强亲电甲基化试剂。

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