Jump to main content
Jump to site search

Issue 4, 1994
Previous Article Next Article

Synthesis, characterization and basicity properties of two new oxa-aza macrobicyclic receptors. Crystal structure of a ‘water cryptate’

Abstract

The synthesis and characterization of the two new oxa-aza macrobicycles 16,21 -dimethyl-4,7,10-trioxa-1,13,16,21-tetraazabicyclo[11.5.5]tricosane (C1) and 19,24-dimethyl-4,7,10,13-tetraoxa-1,16,19,24-tetraazabicyclo[14.5.5] hexacosane (C2) have been reported. Their proton transfer behaviour has been studied in aqueous solution by potentiometry (298.1 ± 0.1 K, I= 0.15 mol dm–3), microcalorimetry and 1H and 13C NMR spectroscopy. Both of them behave as diprotic bases. C1 and C2 behave as strong bases in the first protonation step and as moderate bases in the second one. Their basicity is due to a main enthalpic contribution. NMR experiments indicate that the nitrogen atoms involved in the protonation steps are the methylated ones. The crystal structure of [H2C2·H2O][ClO4]2[space group P21, a= 10.450(2), b= 11.391(2), c= 12.666(3)Å, β= 100.21(2)°, V= 1483.8(5)Å3, Z= 2, R= 0.059 and Rw= 0.052] gives confidence to NMR results, confirming that in the [H2C2·H2O]2+ cation the protons are localized on the methylated nitrogen atoms. Furthermore, a water molecule is enclosed into the macrocyclic cavity, interacting via hydrogen bonds with both protonated nitrogens and three oxygens of the macrocyclic framework and originating a ‘water cryptate’.

Back to tab navigation

Article information


J. Chem. Soc., Perkin Trans. 2, 1994, 815-820
Article type
Paper

Synthesis, characterization and basicity properties of two new oxa-aza macrobicyclic receptors. Crystal structure of a ‘water cryptate’

C. Bazzicalupi, A. Bencini, A. Bianchi, V. Fusi, P. Paoletti and B. Valtancoli, J. Chem. Soc., Perkin Trans. 2, 1994, 815
DOI: 10.1039/P29940000815

Search articles by author

Spotlight

Advertisements