α,α′,α″,α′″-meso-Tetrahexyltetramethyl-calix[4]pyrrole: an easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents

by Neil J. Williams, Vyacheslav S. Bryantsev, Radu Custelcean, Charles A. Seipp, Bruce A. Moyer


α,α′,α″,α′″-meso-Tetrahexyltetramethyl-calix[4]pyrrole is easily obtained as a single diastereomer in a one-pot reaction. It exhibits enhanced solubility in organic solvents, including aliphatic solvents, relative to its parent meso-octamethylcalix[4]pyrrole (1). Somewhat surprisingly, the tetrahexyl derivative 2 complexes with tributylmethylammonium chloride in chloroform more strongly than does 1 as shown by NMR titrations. However, 1 and 2 exhibit comparable complexation strength in extraction experiments, the difference between the NMR and extraction results being attributed to the effect of organic-phase water in the extraction systems. Mass-action analysis indicates the formation of the predominant complex TBMA+(1 or 2)Cl in both NMR and extraction systems, and equilibrium constants are reported. x-Ray crystal structures were obtained for the free ligand 2 and its complex with tetramethylammonium chloride. The free ligand crystallises in the 1,3-alt conformation with equatorial hexyl arms. In the chloride complex with 2 in its cone conformation, the hexyl arms adopt an axial orientation, enveloping the anion. DFT calculations show this binding conformation to be the most stable, mostly owing to destabilising steric interactions involving the pyrrole C–H and alkyl C–H groups positioned equatorially.

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Publication Citation

Supramolecular Chemistry 2016 28 (1-2) pp 176-187
DOI: 10.1080/10610278.2015.1120873