Silver(I) Cation Complexation with 3α,3'α-Bis(pyridine-n-carboxy) Lithocholic Acid 1,2-Ethanediol Diesters (n = 2–4): 1H, 13C and 15N NMR Spectral Studies and Molecular Orbital Calculations

University of Jyväskylä
Journal of Inclusion Phenomena (Impact Factor: 1.49). 09/1999; 35(1):75-84. DOI: 10.1023/A:1008198415212


Three isomeric molecular clefts: 3,3'-bis(pyridine-n-carboxy) lithocholic acid 1,2-ethanediol diesters (n = 2–4) 1–3 have been synthesized and their structures ascertained by 1H, 13C NMR and MALDI TOF MS. Their complex formation with Ag+-cation (added as AgO3 SCF3) have been investigated by means of NMR and molecular orbital calculations. The coordination behaviour of the silver(I) cation is dependent on the isomerism of the pyridine-n-carboxy moiety. In 1 (pyridine-2-carboxylato = picolinato) both NMR and theoretical calculations strongly suggest that the coordination occurs with the lone electron pairs of the pyridine nitrogen and carbonyl oxygen in both of the arms of the molecular cleft separately. In 2 and 3 (pyridine-3-carboxylato = nicotinato and pyridine-4-carboxylato = isonicotinato) where the distance between the pyridine nitrogen and carbonyl oxygen is too large to allow the same type of coordination as in 1, 3-complexation with the pyridine ring and carbonyl oxygen of the different arms of the molecular cleft simultaneously is suggested by molecular orbital calculations and supported also by NMR. No Ag+-cation coordination was observed with the 1,2-ethanediol oxygens in 1–3.

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