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亲电阴离子开启的稀有气体化学新视角。

New Perspectives in the Noble Gas Chemistry Opened by Electrophilic Anions.

作者信息

Rohdenburg Markus, Azov Vladimir A, Warneke Jonas

机构信息

Fachbereich 2-Biologie/Chemie, Institut für Angewandte und Physikalische Chemie, Universität Bremen, Bremen, Germany.

Department of Chemistry, University of the Free State, Bloemfontein, South Africa.

出版信息

Front Chem. 2020 Nov 13;8:580295. doi: 10.3389/fchem.2020.580295. eCollection 2020.

Abstract

Binding of noble gases (NGs) is commonly considered to be the realm of highly reactive electophiles with cationic or at least non-charged character. Herein, we summarize our latest results evidencing that the incorporation of a strongly electrophilic site within a rigid cage-like anionic structure offers several advantages that facilitate the binding of noble gases and stabilize the formed NG adducts. The anionic superelectrophiles investigated by us are based on the -dodecaborate dianion scaffold. The record holder [B(CN)] binds spontaneously almost all members of the NG family, including the very inert argon at room temperature and neon at 50 K in the gas phase of mass spectrometers. In this perspective, we summarize the argumentation for the advantages of anionic electrophiles in binding of noble gases and explain them in detail using several examples. Then we discuss the next steps necessary to obtain a comprehensive understanding of the binding properties of electrophilic anions with NGs. Finally, we discuss the perspective to prepare bulk ionic materials containing NG derivatives of the anionic superelectophiles. In particular, we explore the role of counterions using computational methods and discuss the methodology, which may be used for the actual preparation of such salts.

摘要

稀有气体(NGs)的结合通常被认为是具有阳离子或至少不带电荷特性的高活性亲电试剂的领域。在此,我们总结了我们的最新结果,这些结果表明在刚性笼状阴离子结构中引入强亲电位点具有几个优点,有助于稀有气体的结合并稳定形成的NG加合物。我们研究的阴离子超亲电试剂基于 - 十二硼酸盐二价阴离子支架。创纪录的[B(CN)]几乎能在室温下自发结合稀有气体家族的所有成员,包括非常惰性的氩气,在质谱仪气相中50 K时能结合氖气。从这个角度出发,我们总结了阴离子亲电试剂在结合稀有气体方面的优势论据,并通过几个例子详细解释了这些优势。然后我们讨论了全面理解亲电阴离子与稀有气体结合特性所需的后续步骤。最后,我们讨论了制备含有阴离子超亲电试剂的稀有气体衍生物的块状离子材料的前景。特别是,我们使用计算方法探讨了抗衡离子的作用,并讨论了可用于实际制备此类盐的方法。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7061/7691601/f8bf5d43637a/fchem-08-580295-g0001.jpg

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