A proton complex of p-tert-butylcalix[4]arene-tetrakis(N,N-dimethylthioacetamide): NMR evidence and probable structure

Jaroslav Kriz (1) , Jiri Dybal (2) , Emanuel Makrlik (3) , Petr Vanura (4) , Jan Lang (5)

1 Structure Analysis
2 Structure Analysis
3 Faculty of Sciences
4 ICT - Institute of Chemical Technology [Prague]
5 Faculty of Mathematics and Physics [Praha/Prague]

Using 1H and 13C NMR together with quantum mechanical DFT calculations, we show that p-tert-butylcalix[4]arene-tetrakis(N,N-dimethylthioacetamide) (1) forms a stable equimolecular complex with proton in the form of hydroxonium ion in nitrobenzene-d5. Protons were offered by hydrogen bis(1,2-dicarbollyl) cobaltate (HDCC) and converted to hydroxonium ions by traces of water. The complex 1.H3O+ adopts a slightly asymmetric but rapidly motionally averaged conformation, which is distinctly more cone-like than ligand 1. The hydroxonium ion H3O+ is bound partly to thiocarbonyl sulphur atoms and partly to phenoxy oxygen atoms of 1 by strong hydrogen bonds and other electrostatic interactions.

Mots clés: Physical Sciences

Jaroslav Kriz, Jiri Dybal, Emanuel Makrlik, Petr Vanura, Jan Lang. A proton complex of p-tert-butylcalix[4]arene-tetrakis(N,N-dimethylthioacetamide): NMR evidence and probable structure. Supramolecular Chemistry, 2007, 19 (6), pp.419-424. ⟨10.1080/10610270601089360⟩. ⟨hal-00513497⟩