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Issue 46, 2019
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First experimental evidence for the elusive tetrahedral cations [EP3]+ (E = S, Se, Te) in the condensed phase

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Abstract

Condensed phase access to the unprecedented tetrahedral cations [EP3]+ (E = S, Se, Te) was achieved through the reaction of ECl3[WCA] with white phosphorus ([WCA] = [Al(ORF)4] and [F(Al(ORF)3)2]; –RF = –C(CF3)3). Previously, [EP3]+ was only known from gas phase MS investigations. By contrast, the reaction of ECl3[A] with the known P33− synthon Na[Nb(ODipp)3(P3)] (enabling AsP3 synthesis), led to formation of P4. The cations [EP3]+ were characterized by multinuclear NMR spectroscopy in combination with high-level quantum chemical calculations. Their bonding situation is described with several approaches including Atoms in Molecules and Natural Bond Orbital analysis. The first series of well-soluble salts ECl3[WCA] was synthesized and fully characterized as starting materials for the studies on this elusive class of [EP3]+ cations. Yet, with high [ECl3]+ fluoride ion affinity values between 775 (S), 803 (Se) and 844 (Te) kJ mol−1, well exceeding typical phosphenium ions, these well-soluble ECl3[WCA] salts could be relevant in view of the renewed interest in strong (also cationic) Lewis acids.

Graphical abstract: First experimental evidence for the elusive tetrahedral cations [EP3]+ (E = S, Se, Te) in the condensed phase

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Supplementary files

Article information


Submitted
06 Aug 2019
Accepted
06 Oct 2019
First published
07 Oct 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2019,10, 10779-10788
Article type
Edge Article

First experimental evidence for the elusive tetrahedral cations [EP3]+ (E = S, Se, Te) in the condensed phase

P. Weis, D. C. Röhner, R. Prediger, B. Butschke, H. Scherer, S. Weber and I. Krossing, Chem. Sci., 2019, 10, 10779
DOI: 10.1039/C9SC03915E

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