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The formation of endo-complexes between calixarenes and amines—a reinvestigation

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Abstract

The formation of an endo-complex between p-allylcalix[4]arene and t-butylamine was described by Gutsche in 1985. However, for a comparable system, it has been shown using NOE methods that the amine does not reside inside the calix. Instead, an exo-calix complex is formed. A reevaluation suggests that the previous conclusion is an artifact due to improper NMR-data processing. DFT (RB3LYP/6–31G(d)) calculations confirm the higher stability of the exo-complex over its endo-counterpart.

Calixarenes undergo proton transfer to amines. However, contrary to literature data,no endo-calix complex is formed. This is shown by NMR NOE methods as well asby calculations

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Acknowledgements

We thank Dr. Frank Beierlein and Dr. Nico J. R. van Eikema Hommes for helpful discussions.

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  1. Computer-Chemie-Centrum, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstrasse, 25, 91052, Erlangen, Germany

    Ralph Puchta & Timothy Clark

  2. Institut für Organische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Henkestrasse, 42, 91054, Erlangen, Germany

    Walter Bauer

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  1. Ralph Puchta
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Correspondence to Walter Bauer.

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Dedicated to Professor Dr. Paul von Ragué Schleyer on the occasion of his 75th birthday.

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Puchta, R., Clark, T. & Bauer, W. The formation of endo-complexes between calixarenes and amines—a reinvestigation. J Mol Model 12, 739–747 (2006). https://doi.org/10.1007/s00894-005-0079-6

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