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凝聚相中难以捉摸的四面体阳离子[EP]（E = S、Se、Te）的首个实验证据。

First experimental evidence for the elusive tetrahedral cations [EP] (E = S, Se, Te) in the condensed phase.

作者信息

Weis Philippe, Röhner David Christopher, Prediger Richard, Butschke Burkhard, Scherer Harald, Weber Stefan, Krossing Ingo

机构信息

Institut für Anorganische und Analytische Chemie , Freiburger Materialforschungszentrum (FMF) , Universität Freiburg , Albertstr. 21 , 79104 Freiburg , Germany . Email:

Institut für Physikalische Chemie , Universität Freiburg , Albertstr. 21 , 79104 Freiburg , Germany.

出版信息

Chem Sci. 2019 Oct 7;10(46):10779-10788. doi: 10.1039/c9sc03915e. eCollection 2019 Dec 14.

DOI:10.1039/c9sc03915e
PMID:32055385
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7006506/
Abstract

Condensed phase access to the unprecedented tetrahedral cations [EP] (E = S, Se, Te) was achieved through the reaction of ECl[WCA] with white phosphorus ([WCA] = [Al(OR)] and [F(Al(OR))]; -R = -C(CF)). Previously, [EP] was only known from gas phase MS investigations. By contrast, the reaction of ECl[A] with the known P synthon Na[Nb(ODipp)(P)] (enabling AsP synthesis), led to formation of P. The cations [EP] were characterized by multinuclear NMR spectroscopy in combination with high-level quantum chemical calculations. Their bonding situation is described with several approaches including and analysis. The first series of well-soluble salts ECl[WCA] was synthesized and fully characterized as starting materials for the studies on this elusive class of [EP] cations. Yet, with high [ECl] fluoride ion affinity values between 775 (S), 803 (Se) and 844 (Te) kJ mol, well exceeding typical phosphenium ions, these well-soluble ECl[WCA] salts could be relevant in view of the renewed interest in strong (also cationic) Lewis acids.

摘要

通过使ECl[WCA]与白磷（[WCA] = [Al(OR)]和[F(Al(OR))]；-R = -C(CF)）反应，实现了前所未有的四面体阳离子[EP]（E = S、Se、Te）的凝聚相合成。此前，[EP]仅在气相质谱研究中被知晓。相比之下，ECl[A]与已知的磷合成子Na[Nb(ODipp)(P)]（可用于合成AsP）反应，生成了P。通过多核核磁共振光谱结合高水平量子化学计算对阳离子[EP]进行了表征。采用包括 和 分析在内的多种方法描述了它们的成键情况。合成了第一系列易溶盐ECl[WCA]，并对其进行了全面表征，作为研究这类难以捉摸的[EP]阳离子的起始原料。然而，鉴于对强（也是阳离子型）路易斯酸的新兴趣，这些易溶的ECl[WCA]盐具有一定相关性，其氟离子亲和能值较高，分别为775（S）、803（Se）和844（Te）kJ/mol，远超典型的磷鎓离子。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5b4/7006506/c05d184ba49e/c9sc03915e-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5b4/7006506/fb5db5ddd372/c9sc03915e-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5b4/7006506/04a14ef01be2/c9sc03915e-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5b4/7006506/e417d284bcc7/c9sc03915e-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5b4/7006506/bf2ac07ad558/c9sc03915e-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5b4/7006506/c05d184ba49e/c9sc03915e-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5b4/7006506/fb5db5ddd372/c9sc03915e-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5b4/7006506/04a14ef01be2/c9sc03915e-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5b4/7006506/e417d284bcc7/c9sc03915e-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5b4/7006506/bf2ac07ad558/c9sc03915e-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5b4/7006506/c05d184ba49e/c9sc03915e-f3.jpg

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本文引用的文献

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2
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Nat Commun. 2019 Feb 7;10(1):624. doi: 10.1038/s41467-019-08517-2.
3
Elusive Zintl Ions [μ-HSi ] and [Si ] in Liquid Ammonia: Protonation States, Sites, and Bonding Situation Evaluated by NMR and Theory.
Sci Adv. 2022 Jun 3;8(22):eabo5792. doi: 10.1126/sciadv.abo5792. Epub 2022 Jun 1.
4
Soft interactions with hard Lewis acids: generation of mono- and dicationic alkaline-earth metal arene-complexes by direct oxidation.与硬路易斯酸的软相互作用：通过直接氧化生成单阳离子和双阳离子碱土金属芳烃配合物。
Chem Sci. 2020 Jan 13;11(8):2068-2076. doi: 10.1039/c9sc06254h. eCollection 2020 Feb 28.
液氨中难以捉摸的津特耳离子[μ-HSi]和[Si]：通过核磁共振和理论评估质子化状态、位点及键合情况
Angew Chem Int Ed Engl. 2019 Mar 4;58(10):3133-3137. doi: 10.1002/anie.201812955. Epub 2019 Jan 29.
4
Improving the Global Electrophilicity Index (GEI) as a Measure of Lewis Acidity.改进作为路易斯酸度度量的全球亲电指数（GEI）。
Inorg Chem. 2018 Dec 3;57(23):14764-14771. doi: 10.1021/acs.inorgchem.8b02517. Epub 2018 Nov 13.
5
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Angew Chem Int Ed Engl. 2001 Oct 15;40(20):3910-3912. doi: 10.1002/1521-3773(20011015)40:20<3910::AID-ANIE3910>3.0.CO;2-2.
10
Bi Te -A Cube-Shaped, Polycationic Main Group Element Cluster.铋碲——一种立方体形的聚阳离子主族元素簇合物。
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