Issue 14, 2023

The perfluoroadamantoxy aluminate as an ideal weakly coordinating anion? – synthesis and first applications

Abstract

Weakly coordinating anions (WCAs) facilitate the stabilization and isolation of highly reactive and almost “naked” cations. Alkoxyaluminate-based WCAs such as [Al(OC(CF3)3)4] ([pf]) are widely used due to their synthetic accessibility and their high stability. However, small cations are still able to coordinate the oxygen atoms of the [pf] anion or even to abstract an alkoxy ligand. The novel WCA [Al(OC10F15)4] ([pfAd]; OC10F15 = perfluoro-1-adamantoxy) is characterized by a very rigid core framework, thus indicating a higher stability towards fluoride-ion abstraction (DFT calculations) and providing hope to generate less disordered crystal structures. The [pfAd] anion was generated by the reaction of the highly acidic alcohol perfluoro-1-adamantanol C10F15OH with LiAlH4 in o-DFB. Li[pfAd] could not be synthesized free of impurities (and still contains unreacted alcohol). Yet, starting from contaminated Li[pfAd], the very useful pure salts Ag[pfAd], [Ph3C][pfAd] and [H(OEt2)2][pfAd] could be synthesized. The salts were characterized by NMR spectroscopy, single-crystal X-ray diffraction and IR spectroscopy. Additionally, [NO][pfAd] could be synthesized containing alcohol impurities but nonetheless enabled the synthesis of the salt P9+[pfAd]. The synthesis of Tl[pfAd] in a mixture of H2O/acetone/o-DFB demonstrated the water stability of the [pfAd] anion.

Graphical abstract: The perfluoroadamantoxy aluminate as an ideal weakly coordinating anion? – synthesis and first applications

Supplementary files

Article information

Article type
Paper
Submitted
20 Jan 2023
Accepted
10 Mar 2023
First published
10 Mar 2023
This article is Open Access
Creative Commons BY license

Dalton Trans., 2023,52, 4355-4370

The perfluoroadamantoxy aluminate as an ideal weakly coordinating anion? – synthesis and first applications

A. Billion, M. Schorpp, R. Feser, M. Schmitt, L. Eisele, H. Scherer, T. Sonoda, H. Kawa, B. Butschke and I. Krossing, Dalton Trans., 2023, 52, 4355 DOI: 10.1039/D3DT00199G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements